High-stretch energy curable inks &amp; method of use in heat transfer label applications

ABSTRACT

Provided are energy curable high-stretch inks and coatings for heat transfer labels. The inks and coatings include monofunctional monomers/oligomers, thermoplastic inert resins, and zero or a limited amount of multifunctional monomers/oligomers and exhibit good stretchability and surface resistance, such as scratch resistance and solvent (water, oil) resistance. Also provided are methods of using the high stretch inks in heat-transfer label (HTL) applications.

RELATED APPLICATION

Benefit of priority is claimed to U.S. Provisional Application Ser. No.61/513,727, filed Aug. 1, 2011, entitled “HIGH-STRETCH ENERGY CURABLEINKS & METHOD OF USE IN HEAT TRANSFER LABEL APPLICATIONS,” to YuemeiZhang, Nicholas Tulling, Jitendra Modi, Leonard Davis and StephenAnthony Hall.

Where permitted, the subject matter of the above-referenced provisionalapplication is incorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The present invention relates generally to heat-transfer labels and moreparticularly to heat-transfer labels that include inks and coatings thatexhibit good stretchability.

BACKGROUND

Heat-transfer labels (HTLs) are commonly used in the decorating and/orlabeling of commercial articles, such as, and without limitation to,containers for beverages (including alcoholic beverages, such as beer),foods, essential oils, detergents, adverse chemicals, as well as healthand beauty aids. A heat-transfer label (HTL) generally includes acarrier web, a release layer of wax or non-wax coat applied to thecarrier web, and an ink image printed on the release layer. The inkimage is typically transferred to articles by application of heat andpressure, as described in U.S. Pat. No. 3,616,015, one of the most wellknown patents on heat transfer technology. UV and heat curable heattransfer labels are known in the art (e.g., see U.S. Pat. Nos.4,231,742; 4,624,891; 5,342,725; 5,800,656; 6,042,676; 6,391,415;6,423,406; 6,509,075; 7,014,895; 7,160,411 and U.S. Pat. Appl. Pub. No.20120070595).

Commercially available HTL inks generally are solvent-based orwater-based systems. Mandates issued by many governments to limit thevolatile organic compounds (VOCs) used in industry, however, havetriggered development of ultraviolet (UV) and electron beam (EB) curableinks due to their nearly 100% active components and minimal VOCs. Suchsystems are considered more environmentally friendly. Since the energycurable systems do not depend on evaporation of a solvent, processcontrol can be maintained even if a coating or printing machine needs tobe stopped during application. In addition, UV/EB curable inks alsoexhibit much better water resistance than water-based systems. Energyconsumed in the drying process for UV/EB inks and coatings is lower thanenergy consumed in traditional oven drying of water-based orsolvent-based inks and coatings. The increased speed of curing ofradiation curing also reduces production time and thus increasesefficiency.

Container design has evolved from generally cylindrical containers tocontainers that are tapered, contoured, curved or variously shaped.These contours and variation in shape of the container can lead todifficulties in application of a heat transfer label.

Traditional inks and coating do not exhibit sufficient stretch,flexibility and/or extension to conform to the various shapes of somemodern container designs that include more contours and unusual shapeswithout cracking or forming substantial defects in the heat transferlabel or decoration.

Accordingly, a need exists for energy curable inks and/or coatingcompositions that exhibit good stretchability for use in formingflexible and extensible cured inks and coatings, such as for use in heattransfer labels. There is also a need for a sufficiently flexible andextensible heat transfer label formed from one or more curable inksand/or compositions that are adaptable for the more unusual shapes andcontours of modern containers and efficient and economic methods ofapplying heat transfer labels.

SUMMARY OF THE INVENTION

Provided are high-stretch energy curable inks and coatings and methodsfor the fabrication of heat-transfer label applications for use in thedecorating and/or labeling of commercial articles and other applicationsusing the high-stretch energy curable inks and coatings. Also providedare energy curable lithographic inks that demonstrate good lithoprintability, fast cure, and stretch 25% or more without cracking whenprinted up to 5 layers with multi color traps with or without first downclear coating and with or without last down white. Also provided areenergy curable inks and their use in heat-transfer label (HTL)applications and more particularly to methods of using the UV/EB curableoffset inks in multi-layer HTL applications that require high stretchduring the heat-transfer process, which is required by some moderncontainer designs that include more unusual shapes. Also provided areenergy curable inks and coatings that when cured are resistant toabrasion, water, chemicals, and heat, and exhibit good flexibility andextensibility. Also provided are heat transfer labels containing one ormore layers of the stretchable inks and/or coatings provided herein. Theheat transfer labels can include a carrier, such as a carrier film, onwhich the heat transfer label is supported. The heat transfer label alsocan include a release layer that facilitates separation of the heattransfer label from the carrier when the heat transfer label is appliedto a container.

Also provided are energy curable inks and/or coating compositions thatform flexible, stretchable inks and/or coatings when cured, and thecured inks and/or coatings formed therefrom. The ink compositions and/orcoating compositions can include 80 wt % or greater monofunctionalmonomers/oligomers and inert resins, such as inert thermoplastic resinsor a combination thereof, and 20 wt % or less of multifunctionalmonomers and oligomers and, optionally, a viscosity modifier and/orother additives. The viscosity modifier can be a monofunctional monomer,a thermoplastic resin, or any combination thereof. The ink and/orcoating compositions can be cured using any suitable actinic radiation,e.g., ultraviolet (UV) light or electron beam (EB) radiation.

Also provided are methods of labeling or decorating a container with aflexible and extensible heat transfer label. Exemplary methods caninclude as steps printing at least one layer of an energy curable ink orcoating provided herein on the release side of a carrier film, curingthe at least one layer of energy curable ink or coating using actinicradiation to produce a cured print, forming the cured print into a heattransfer label, and applying the heat transfer label to a substrate,where the heat transfer label can stretch 25% or more without cracking.Also provided are containers labeled and/or decorated with a flexibleand extensible heat transfer label as described herein.

DETAILED DESCRIPTION OF THE INVENTION

It is to be understood that the foregoing general description and thefollowing detailed description are exemplary and explanatory only andare not restrictive of any subject matter claimed.

The section headings used herein are for organizational purposes onlyand are not to be construed as limiting the subject matter described.

I. DEFINITIONS

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of skill in theart to which the inventions belong. All patents, patent applications,published applications and publications, websites and other publishedmaterials referred to throughout the entire disclosure herein, unlessnoted otherwise, are incorporated by reference in their entirety for anypurpose.

In this application, the use of the singular includes the plural unlessspecifically stated otherwise. In this application, the use of “or”means “and/or” unless stated otherwise. As used herein, use of the term“including” as well as other forms, such as “includes,” and “included,”is not limiting.

As used herein, ranges and amounts can be expressed as “about” aparticular value or range. “About” is intended to also include the exactamount. Hence “about 5 percent” means “about 5 percent” and also “5percent.” “About” means within typical experimental error for theapplication or purpose intended.

As used herein, “optional” or “optionally” means that the subsequentlydescribed event or circumstance does or does not occur, and that thedescription includes instances where said event or circumstance occursand instances where it does not. For example, an optional component in asystem means that the component may be present or may not be present inthe system.

As used herein, the words “a” or “an” are to be taken to include boththe singular and the plural. Conversely, any reference to plural itemsshall, where appropriate, include the singular.

As used herein, “multifunctional” means having two or more functionalgroups.

A multifunctional monomer, e.g., can be a di-functional, tri-functional,tetrafunctional or have a higher number of functional groups. Forexample, a multifunctional acrylate includes diacrylates, triacrylatesand tetraacrylates.

As used herein, the term “stretch” refers to extending or elongating orincreasing in dimension.

As used herein, the term “stretchability” refers to the ability of amaterial to be stretched in dimension.

As used herein, “blend” refers to a combination of two or morecomponents. As used herein, “% stretch” refers to the percentageincrease in dimension. For example, if the length of a test portion of alabel is measured at 1 inch before stretch and then 1.25 inches afterstretch, it is said to have been stretched by or to exhibit a stretch of25% (an increase in length of 25% based on the original length). Thephrase “25% stretch” means that the original dimension, e.g. length,increased by 25%.

As used herein, “high stretch” refers to a %>stretch of at least20%>stretch without cracking.

As used herein, the phrase “without cracking” means no visual signs ofcracking are observed when inspected visually without the aid of anyinstrument.

As used herein, the term “inert resin” refers to a resin that does notreact with monomers/oligomers in the resin composition.

As used herein, the term “thermoplastic resin” refers to an inert resincontaining organic polymer compounds, which can include linear polymers,where the inert resin exhibits its plasticity upon heating.

As used herein, “monomer” refers to a material having a viscosity lessthan that of an oligomer and a relatively low molecular weight (i.e.,having a molecular weight less than about 750 g/mole) and containing oneor more polymerizable groups, which are capable of polymerizing andcombining with other monomers or oligomers to form other oligomers orpolymers. A monomer can have a viscosity of 150 cP or less measured at25° C. at a shear rate of about 4 to 20 sec″1 with a Brookfieldviscometer. A monomer can be used to modulate the viscosity of anoligomer.

As used herein, “oligomer” refers to a material having a viscositygreater than that of a monomer and a relatively intermediate molecularweight (i.e., having a molecular weight greater than about 750 g/molebut generally less than 100,000 g/mole) having one or more radiationpolymerizable groups, which are capable of polymerizing and combiningwith monomers or oligomers to form other oligomers or polymers. Thenumber average molecular weight of the oligomer is not particularlylimited and can be, for example, between about 750-10,000 g/mole.Molecular weight can be selected to achieve the desired viscosity,modulus, solvent resistance and other important properties.

Oligomer molecular weight and its distribution can be determined by gelpermeation chromatography.

As used herein, “polymer” refers to a high viscosity molecule comprisinga substructure formed from one or more monomeric, oligomeric, and/orpolymeric constituents polymerized or cross-linked together. The monomerand/or oligomer units can be regularly or irregularly arranged and aportion of the polymer chemical structure can include repeating units.

As used herein, the term “molecular weight” means number averagemolecular weight unless expressly noted otherwise.

As used herein, “cure” or “curing” refers to a process that leads topolymerizing, hardening and/or cross-linking of monomer and/or oligomerunits to form a polymer. Curing can occur via any polymerizationmechanism, including, e.g., free radical routes, and/or in whichpolymerization is photoinitiated, and can include the use of a radiationsensitive photoinitiator.

As used herein, the terms “curable resin,” “curable ink” and “curablecoating” refer to an ability of a resin, ink and coating, respectively,to polymerize, harden, and/or cross link in response to suitable curingstimulus such as ultraviolet (UV) energy, infrared (IR) energy, lightemitting diode (LED) energy, electron beam (EB) energy, heat energy, orother source of energy, with appropriate initiators included in theresin, ink or coating if required. A curable resin, ink or coatingtypically is liquid at 25° C. prior to curing. A curable resin can be acomponent of a curable ink or coating, and a curable ink or curablecoating is used to print a substrate, forming a film of printed ink orcoating. The film of curable ink or coating then is cured, hardening,polymerizing and/or cross-linking the ink or coating to form a cured inkor coating.

As used herein, the term “cured ink” or “cured coating” refers to acurable ink or coating that has been polymerized. In a cured ink orcoating, the curable components of a curable ink or curable coatingreact upon curing to form a polymerized or cross-linked network. Oncuring, the liquid or fluid curable ink or coating cross-links,polymerizes and/or hardens to form a film of cured ink or cured coating.When the curable ink or curable coating cures from a liquid state to asolid state, the curable monomers and/or oligomers form (1) chemicalbonds, (2) mechanical bonds, or (3) a combination of a chemical andmechanical bonds. As a result, the cured high stretch ink or coatingprovided herein can undergo stretching of 25% or more without cracking.

As used herein, “radiation curable” refers to curing in response toexposure to suitable radiation such as ultra violet (UV) radiation,light emitting diode (LED) energy, infrared or electron beam radiation.The term “radiation curable” is intended to cover all forms of curingupon exposure to a radiation source. The energy source used to initiatecrosslinking of the radiation-curable components of the composition canbe actinic, such as radiation having a wavelength in the ultraviolet orvisible region of the spectrum; accelerated particles, such as electronbeam radiation; or thermal, such as heat or infrared radiation. Suitablesources of actinic radiation include mercury lamps, xenon lamps, carbonarc lamps, tungsten filament lamps, lasers, light emitting diodes,sunlight, and electron beam emitters. The curing light can be filteredor focused.

Throughout this disclosure, all parts and percentages are by weight (wt% or mass % based on the total weight) and all temperatures are in ° C.,unless otherwise indicated.

II. HIGH-STRETCH ENERGY CURABLE INK AND COATING COMPOSITIONS

The present application is directed to a set of novel energy curableinks and coatings, including litho inks, and a method of providing heattransfer labels (HTL) that can withstand 25% stretch or more, withoutcracking, printed up to 5 layers trap (5 layers of trapped ink) withmulti color traps with first down clear coating and with or without lastdown white. For the purposes of the present application, a passingresult for stretch is when there is no visual evidence of cracking. Afailing result is when there is visual evidence of cracking, even if thecracks are small. This represents a significant improvement overcommercially available inks as shown in the Examples. The UV curableinks and coatings provided herein contains zero, or very limitedamounts, of multifunctional monomers/oligomers while still providingacceptable surface resistance (such as scratch resistance and solvent(water, oil) resistance) and 25% or more stretchability. This is verydifferent from current commercial products, which are mainly composed ofmultifunctional monomers/oligomers which are utilized for the fastestcure speed. The novel HTL offset ink system and method of use is mainlycomposed of fast curing monofunctional monomers/oligomers, such asacrylate/methacrylate monofunctional monomers/oligomers, and inertthermoplastic resins that do not react with the monomers/oligomers forthe best stretchability.

The present application relates mainly to free radical UV lithographicinks, however, the resin composition provided herein can be used forformulating other inks including offset, flexo, gravure, or any othertype of printing ink system for HTL application that has a requirementfor ink stretchability during label transfer process under heat. Thehigh-stretch energy curable compositions are not limited to free radicalUV curable ink and coating systems. The high-stretch energy curablecompositions can be formulated for cationic systems and for EB curingand all other actinic curing systems as well. In addition, thehigh-stretch energy curable compositions are not limited to(meth)acrylate materials or free radical polymerization. Thehigh-stretch energy curable compositions can be formulated for cationicepoxy systems and many other polymerizable functional groups as long asthe cured polymer is a thermoplastic polymer. Though there are examplesof specific UV litho inks in the present application, the method ofproviding heat transfer labels that will stretch 25% or more withoutcracking encompasses other ink types as well.

The high-stretch energy curable compositions provided herein include aresin composition and optionally other ingredients, such as one or morecolorants, one or more inhibitors, one or more viscosity modifiers, oneor more photoinitiators and one or more additives. In clear coatcompositions, colorants can be excluded, although in some applications,optical brighteners or other colorants can be included. For example, dyeor pigments or both can be included to provide pigmented coatings toprovide a clear coat of a specific color or shade, or to produce apearlescent or metallic effect. In white ink formulations, mineralpigments, such as Ti02, can be included. The resin compositions includedin the high-stretch energy curable compositions, as described below,generally contain 80 wt % or greater monofunctional monomers/oligomersand inert thermoplastic resins or a combination thereof. Energy curablecompositions, such as inks and coatings, that include the provided resincompositions, when cured are capable of being stretched 25% or morewithout any visual cracking at varied color densities and when presentas single or multiple layers in a heat transfer label.

A. Resin Compositions

Provided are resin compositions for energy curable compositions. Theresin compositions provided herein exhibit high stretch after curing andare suitable for applications in which stretchability of thecompositions is desirable. An example of an application wherestretchability of the composition is desirable is heat transfer labels.It has been determined that resin compositions containing 80 wt % orgreater monofunctional monomers/oligomers and inert thermoplastic resinsor a combination thereof and 20 wt % or less of multifunctional monomersand oligomers, such as di-, tri-, tetra or higher functional groups (2or more functional groups) can be used in energy curable inks and/orcoatings, which cure at acceptable rates and produce heat transferlabels and decorations that are capable of being stretched 25% or morewithout any visual cracking at varied color densities and at single ormultiple layers. The resin compositions can be 80 wt % or greater of asolution of inert resin in monofunctional monomers/oligomers.

1. Monofunctional Monomers/Oligomers

The monofunctional monomers/oligomers in the resin compositions providedherein are selected to be compatible with the other materials in thecomposition, to promote fast cure speed, and to produce coatings thatare tack free under normal curing conditions on a commercial press. Themonofunctional monomers/oligomers preferably have a Tg above 0° C., suchas in the range of 10° C. to 100° C. In some applications, themonofunctional monomers/oligomers are selected to have a Tg at or aboutroom temperature (20° C.-25° C.).

For the high-stretch energy curable inks and coating compositionsprovided herein formulated for lithographic application, themonofunctional monomers/oligomers and inert resins are selected to yieldan ink or coating with good fountain compatibility and lithographicproperties.

In some applications, the monofunctional monomers/oligomers and resinsin the inks of the present application exhibit tack in the range of8-20, or in the range of 10-16.

The resin compositions can contain 80 wt % or greater monofunctionalmonomers/oligomers. In some applications, the amount of monofunctionalmonomers/oligomers can be between 80 wt % and 99 wt % of the resincomposition.

In some applications, the amount of monofunctional monomers/oligomers inthe resin composition is greater than 85 wt %, or greater than 90 wt %or greater than 95 wt % based on the total weight of the resincomposition. In some applications, monofunctional monomers ormonofunctional oligomers or a combination thereof are present in a rangebetween 85 wt % and 99 wt %, or in a range between 90 wt % and 99.5 wt%.

In some applications, the amount of monofunctional monomers ormonofunctional oligomers or a combination thereof in the resincomposition can be greater than 20 wt %, or greater than 25 wt %, orgreater than 30 wt %, or greater than 35 wt %, or greater than 40 wt %,or greater than 45 wt %, or greater than 50 wt %, or greater than 55 wt%, or greater than 60 wt %, or greater than 65 wt %, or greater than 70wt %, or greater than 75 wt %, or greater than 80 wt %, or greater than85 wt %, or greater than 90 wt %, based on the total weight of the resincomposition. In some applications, monofunctional monomers or monofunctional oligomers or a combination thereof are present in an amountthat is 50 wt %, 50.5 wt %, 51 wt %, 51.5 wt %, 52 wt %, 52.5 wt %, 53wt %, 53.5 wt %, 54 wt %, 54.5 wt %, 55 wt %, 55.5 wt %, 56 wt %, 56.5wt %, 57 wt %, 57.5 wt %, 58 wt %, 58.5 wt %, 59 wt %, 59.5 wt %, 60 wt%, 60.5 wt %, 61 wt %, 61.5 wt %, 62 wt %, 62.5 wt %, 63 wt %, 63.5 wt%, 64 wt %, 64.5 wt %, 65 wt %, 65.5 wt %, 66 wt %, 66.5 wt %, 67 wt %,67.5 wt %, 68 wt %, 68.5 wt %, 69 wt %, 69.5 wt %, 70 wt %, 70.5 wt %,71 wt %, 71.5 wt %, 72 wt %, 72.5 wt %, 73 wt %, 73.5 wt %, 74 wt %,74.5 wt %, 75 wt %, 75.5 wt %, 76 wt %, 76.5 wt %, 77 wt %, 77.5 wt %,78 wt %, 78.5 wt %, 79 wt %, 79.5 wt %, 80 wt %, 80.5 wt %, 81 wt %,81.5 wt %, 82 wt %, 82.5 wt %, 83 wt %, 83.5 wt %, 84 wt %, 84.5 wt %,85 wt %, 85.5 wt %, 86 wt %, 86.5 wt %, 87 wt %, 87.5 wt %, 88 wt %,88.5 wt %, 89 wt %, 89.5 wt %, 90 wt %, 90.5 wt %, 91 wt %, 91.5 wt %,92 wt %, 92.5 wt %, 93 wt %, 93.5 wt %, 94 wt %, 94.5 wt %, 95 wt %,95.5 wt %, 96 wt %, 96.5 wt %, 97 wt %, 97.5 wt %, 98 wt %, 98.5 wt %,99 wt % or 99.5 wt % by weight of the resin composition.

The ratio of monofunctional monomer to monofunctional oligomer, whenpresent, can vary from 100:1 to 100:1, including all permutationstherebetween. For example, the ratio of the amount of monofunctionalmonomer to monofunctional oligomer can be 10:1, 9:1, 8:1, 7:1, 6:1, 5:1,4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

Examples of monofunctional monomers/oligomers in the resin compositionsprovided herein include acrylate esters, acrylic esters, acrylicmonomer, N-acryloyl amine, N-acryloyl morpholine, aliphatic monoacrylate, aliphatic mono methacrylate, alkoxylated lauryl acrylate,alkoxylated phenol acrylate, alkoxylated tetrahydrofurfuryl acrylate,Ci2-Ci4 alkyl methacrylate, aromatic acrylate monomer, aromaticmethacrylate monomer, benzyl methacrylate, caprolactone acrylate, cyclictrimethylolpropane formal acrylate, cycloaliphatic acrylate monomer,dicyclopentadienyl methacrylate, diethylene glycol methyl ethermethacrylate, epoxy acrylate, epoxy methacrylate, 2(2-ethoxy-ethoxy)ethyl acrylate, ethoxylated (4) nonyl phenol acrylate, ethoxylated (4)nonyl phenol methacrylate, ethoxylated nonyl phenol acrylate,2-ethylhexyl methacrylate, isobomyl acrylate, isobomyl methacrylate,isodecyl acrylate, isodecyl acrylate, isodecyl methacrylate, isooctylacrylate, isooctyl acrylate, lauryl acrylate, lauryl methacrylate,methoxy polyethylene glycol (350) monoacrylate, methoxy polyethyleneglycol (350) monomethacrylate, methoxy polyethylene glycol (550)monoacrylate, methoxy poly-ethyl ene glycol (550) monomethacrylate,nonylphenylpolyoxyethylene acrylate, octyldecyl acrylate, 2-phenoxyethylacrylate, 2-phenoxyethyl methacrylate, polyester acrylate,polyester(meth)acrylate, polyether acrylate, polyether methacrylate,polyphenoxy acrylates, stearyl acrylate, stearyl methacrylate,tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tridecylacrylate, tridecyl methacrylate, triethylene glycol ethyl ethermethacrylate, 3,3,5-trimethylcyclohexyl methacrylate,3,3,5-trimethyl-cyclo-hexyl methacrylate, urethane acrylate, urethanemethacrylate, urethane oligomer, an acrylated diol oligomer (e.g.,SARTOMER 2000 oligomer, an unsaturated aliphatic ester which is a polyolpolyacrylate), an oligomer in which a (meth)acryloyl group is bound toone terminal of polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate,poly-z-butyl(meth)acrylate or polystyrene (e.g., a polystyrene oligomerhaving a methacryloyl group at one terminal (Mn=6000, trade name: AS-6,manufactured by Toagosei Co., Ltd.), a polymethyl methacrylate oligomerhaving a methacryloyl group at one terminal (Mn=6000, trade name: AA-6,manufactured by Toagosei Co., Ltd.), and a poly-n-butylacrylate oligomerhaving a methacryloyl group at one terminal (Mn=6000, trade name: AB-6,manufactured by Toagosei Co., Ltd.), polyurethane acrylate oligomer,polyurethane methacrylate oligomer, one-end methacryloylated polymethylmethacrylate oligomer, one-end methacryloylated polystyrene oligomer,one-terminal-end methacryloylated polyethylene glycol, epoxymethacrylate, polyether methacrylate, polyester methacrylate,polyurethane methacrylate, polyol methacrylates, melamine methacrylate,ethoxylated trimethanolpropane methacrylate, ethoxylateddi(trimethanol-propane) methacrylate, ethoxylated pentaerythritolmethacrylate, ethoxylated dipentaerythritol methacrylate, ethoxylatedneopentaglycol methacrylate, ethoxylated propylene glycol methacrylate,polyethylene glycol dimethacrylate, epoxy acrylate, polyether acrylate,polyester acrylate, polyurethane acrylate, polyol acrylates, propyleneglycol acrylate, alkanediol acrylate, trimethylol propane acrylate,glycerolpropoxy acrylate, pentaerythritrol acrylate, neopentaglycolacrylate, N-vinyl amide, N-vinyl-formamide and N-vinyl-pyrrolidone, andcombinations thereof. In some applications, the resin compositionincludes acrylate or methacrylate monomers or oligomers or combinationsthereof.

2. Inert Resins

The high-stretch energy curable resin compositions provided herein caninclude one or more inert resins. Preferred inert resins arethermoplastic resins. Particularly preferred are thermoplastic resinshaving a Tg of 0 to 300° C., more preferably a Tg of at or about 20° C.to 100° C. or 25° C. to 75° C. In some applications, the monofunctionalmonomers/oligomers are selected to have a Tg of at or about roomtemperature (at or about 20° C. to 25° C.) or greater.

A non-limiting list of exemplary thermoplastic resin types includeacrylic resins, urea aldehyde resins, polyester resins, aldehyde resins,epoxy resins, rosin ester resins, cellulose nitrate, celluloseacetobutyrate, vinyl chloride copolymers, melamine-formaldehyde resins,polyurethane resins, polyimide resins, alkyd resins, and phthalateresins, including aliphatic and aromatic types. Typical examples of thethermoplastic resin include synthetic rubber latex such asstyrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methylmethacrylate-butadiene copolymer, styrene-acrylonitrile-butadienecopolymer and styrene-methyl methacrylate-butadiene copolymer andmodified versions thereof, such as amino-modified, polyether-modified,epoxy-modified, aliphatic acid-modified, carbonyl-modified andcarboxy-modified resins, styrene-maleic anhydride copolymer, methylvinyl ether-maleic anhydride copolymer, polyacrylic acid copolymer,polystyrene, styrene/acrylic acid ester copolymer, polyacrylic acidester, polymethacrylic acid ester, acrylic acid ester/acrylic acid estercopolymer, and low-melting-point polyamide resin. A single type ofthermoplastic resin can be used, or a combination of two or more typesof thermoplastic resin can be included in the high stretch energycurable resin compositions. An exemplary urea aldehyde resin is Laropal®A81 from BASF, which is among the preferred thermoplastic resins.

When the resin compositions provided herein contain one or more inertresins, the inert resin can be present in an amount of at or about 10 wt% or greater based on the weight of the resin composition. In someapplications, the amount of inert resin can be 10 wt % or less based onthe weight of the resin composition. In some applications, the amount ofinert resin can be between 10 wt % and 90 wt % based on the weight ofthe resin composition. In some applications, the amount of inert resinin the resin composition can be between 15 wt % and 85 wt %, or between20 wt % and 80 wt %, or between 25 wt % and 75 wt %, or between 30 wt %and 70 wt %, or between 35 wt % and 65 wt %, or between 40 wt % and 60wt %, or between 10 wt % and 50 wt %, or between 50 wt % and 95 wt %, orbetween 1 wt % and 10 wt %, based on the weight of the resincomposition. In some applications, the amount of inert resin in theresin composition can be greater than 1 wt %, or greater than 5 wt %, orgreater than 10 wt %, or greater than 15 wt %, or greater than 20 wt %,or greater than 25 wt %, or greater than 30 wt %, or greater than 35 wt%, or greater than 40 wt %, or greater than 45 wt %, or greater than 50wt %, or greater than 55 wt %, or greater than 60 wt %, or greater than65 wt %, or greater than 70 wt %, or greater than 75 wt %, or greaterthan 80 wt %, or greater than 85 wt %, or greater than 90 wt %, based onthe total weight of the resin composition. In some applications, inertresin is present in an amount that is 40 wt %, 40.5 wt %, 41 wt %, 41.5wt %, 42 wt %, 42.5 wt %, 43 wt %, 43.5 wt %, 44 wt %, 44.5 wt %, 45 wt%, 45.5 wt %, 46 wt %, 46.5 wt %, 47 wt %, 47.5 wt %, 48 wt %, 48.5 wt%, 49 wt %, 49.5 wt %, 50 wt %, 50.5 wt %, 51 wt %, 51.5 wt %, 52 wt %,52.5 wt %, 53 wt %, 53.5 wt %, 54 wt %, 54.5 wt %, 55 wt %, 55.5 wt %,56 wt %, 56.5 wt %, 57 wt %, 57.5 wt %, 58 wt %, 58.5 wt %, 59 wt %,59.5 wt %, 60 wt %, 60.5 wt %, 61 wt %, 61.5 wt %, 62 wt %, 62.5 wt %,63 wt %, 63.5 wt %, 64 wt %, 64.5 wt %, 65 wt %, 65.5 wt %, 66 wt %,66.5 wt %, 67 wt %, 67.5 wt %, 68 wt %, 68.5 wt %, 69 wt %, 69.5 wt %,70 wt %, 70.5 wt %, 71 wt %, 71.5 wt %, 72 wt %, 72.5 wt %, 73 wt %,73.5 wt %, 74 wt %, 74.5 wt %, 75 wt %, 75.5 wt %, 76 wt %, 76.5 wt %,77 wt %, 77.5 wt %, 78 wt %, 78.5 wt %, 79 wt %, 79.5 wt %, 80 wt %,80.5 wt %, 81 wt %, 81.5 wt %, 82 wt %, 82.5 wt %, 83 wt %, 83.5 wt %,84 wt %, 84.5 wt %, 85 wt %, 85.5 wt %, 86 wt %, 86.5 wt %, 87 wt %,87.5 wt %, 88 wt %, 88.5 wt %, 89 wt %, 89.5 wt %, 90 wt %, 90.5 wt %,91 wt %, 91.5 wt %, 92 wt %, 92.5 wt %, 93 wt %, 93.5 wt %, 94 wt %,94.5 wt %, 95 wt %, 95.5 wt %, 96 wt %, 96.5 wt %, 97 wt %, 97.5 wt %,98 wt %, 98.5 wt %, 99 wt % or 99.5 wt % by weight of the resincomposition.

The ratio of inert resin, when present, to the monofunctionalmonomer/oligomer, can vary from 100:1 to 100:1, including allpermutations therebetween. For example, the ratio of the amount of inertresin to monofunctional monomer/oligomer can be 1:1, 1:2, 1:3, 1:4, 1:5,1:6, 1:7, 1:8, 1:9, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80,1:90, 90:1, 80:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, 2:3, 5:7,7:5, 3:2, 9:1. 8:1, 7:1, 6:1, 5:1, 4:1, 3:1 and 2:1.

In some applications, the amount of monofunctional monomers/oligomers inthe resin composition is 60 wt % or greater and the amount of inertresin is 40 wt % or less. In some applications, the amount ofmonofunctional monomers/oligomers in the resin composition is 70 wt % orgreater and the amount of inert resin is 20 wt % or less. In someapplications, the amount of monofunctional monomers/oligomers in theresin composition is 80 wt % or greater and the amount of inert resin is20 wt % or less. In some applications, the amount of monofunctionalmonomers/oligomers in the resin composition is 85 wt % or greater andthe amount of inert resin is 15 wt % or less. In some applications, theamount of monofunctional monomers/oligomers in the resin composition is90 wt % or greater and the amount of inert resin is 10 wt % or less. Insome applications, the amount of monofunctional monomers/oligomers inthe resin composition is 95 wt % or greater and the amount of inertresin is 5 wt % or less based on the total weight of the resincomposition.

In some applications, the amount of monofunctional monomers/oligomers inthe resin composition is 40 wt % or less and the amount of inert resinis 60 wt % or greater. In some applications, the amount of inert resinin the resin composition is 70 wt % or greater and the amount ofmonofunctional monomers/oligomers is 20 wt % or less. In someapplications, the amount of inert resin in the resin composition is 80wt % or greater and the amount of monofunctional monomers/oligomers is20 wt % or less. In some applications, the amount of inert resin in theresin composition is 85 wt % or greater and the amount of monofunctionalmonomers/oligomers is 15 wt % or less. In some applications, the amountof inert resin in the resin composition is 90 wt % or greater and theamount of monofunctional monomers/oligomers is 10 wt % or less. Theinert resin can be dissolved or solvated by the monofunctionalmonomers/oligomers. In some applications, the resin composition includes80% or greater of a solution comprising inert resin dissolved orsolvated in monofunctional monomers/oligomers.

3. Multifunctional Monomers/Oligomers

The resin composition of the present application can containmultifunctional monomers/oligomers in combination with the blendcontaining inert resins and monofunctional monomers/oligomers, such as aresin blend including a solution containing 80 wt % or greater ofmonofunctional monomers or monofunctional oligomers or inertthermoplastic resins or a combination thereof, e.g., acrylate and/ormethacrylate monomers and/or oligomers and/or inert thermoplasticresins. Ink compositions of the present application that include theresin composition of the present application when cured are capable ofbeing stretched 25% or more without any visual cracking at varied colordensities and at single or multiple layers. Ink compositions of thepresent application will preferably include a resin composition asdescribed above containing <20%, more preferably <10%, more preferably<5%, most preferably 0% multifunctional monomers/oligomers. Commerciallyavailable heat transfer inks contain a high percentage (25% or more)multifunctional monomers/oligomers in order to achieve fast cure speeds.As the amount of multi-functional monomers/oligomers increases, theamount of expected crosslinking increases. The increase in cross-linkingenhances surface resistance properties (increases scratch and waterresistance as well as solvent resistance) but also decreases flexibilityand stretchability. If difunctional and multifunctionalmonomers/oligomers, e.g., di-, tri-, tetra- or higher acrylate and/ormethacrylate monomers/oligomers, are included in the resin composition,for example, to improve crosslink density and/or resistance properties,the multifunctional monomers/oligomers preferably are included inamounts <20 wt %, more preferably <10 wt % or <5 wt %, and particularly0 wt %, based on the weight of the resin composition. In someapplications, the amount of multifunctional monomers/oligomers presentin the resin composition is 0%, 0.05 wt %, 0.1 wt %, 0.2 wt %, 0.3 wt %,0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %, 1.25wt %, 1.5 wt %, 1.75 wt %, 2 wt %, 2.25 wt %, 2.5 wt %, 2.75 wt %, 3 wt%, 3.25 wt %, 3.5 wt %, 3.75 wt %, 4 wt %, 4.25 wt %, 4.5 wt %, 4.75 wt%, 5%, 5.25 wt %, 5.5%, 5.75 wt %, 6 wt %, 6.25 wt %, 6.5 wt %, 6.75 wt%, 7 wt %, 7.25 wt %, 7.5 wt %, 7.75 wt %, 8 wt %, 8.25 wt %, 8.5 wt %,8.75 wt %, 9 wt %, 9.25 wt %, 9.5 wt %, 9.75 wt %, 10 wt %, 11 wt %,11.25 wt %, 11.5 wt %, 11.75 wt %, 12 wt %, 12.25 wt %, 12.5 wt %, 12.75wt %, 13 wt %, 13.25 wt %, 13.5 wt %, 13.75 wt %, 14 wt %, 14.25 wt %,14.5 wt %, 14.75 wt %, 15%, 15.25 wt %, 15.5%, 15.75 wt %, 16 wt %,16.25 wt %, 16.5 wt %, 16.75 wt %, 17 wt %, 17.25 wt %, 17.5 wt %, 17.75wt %, 18 wt %, 18.25 wt %, 18.5 wt %, 18.75 wt %, 19 wt %, 19.25 wt %,19.5 wt %, 19.75 wt % or 20 wt %, based on the weight of the resincomposition.

In some applications, the multifunctional monomer/oligomer isdifunctional. Examples of difunctional monomer/oligomer that can beincluded in the resin composition include alkoxylated aliphaticdiacrylate, alkoxylated aliphatic dimethacrylate, alkoxylated neopentylglycol diacrylate, alkoxylated neopentyl glycol dimethacrylate,1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butyleneglycol diacrylate, 1,3-butylene glycol dimethacrylate, cyclohexanedimethanol diacrylate, cyclohexane dimethanol dimethacrylate, diethyleneglycol diacrylate, diethylene glycol dimethacrylate, dipropylene glycoldiacrylate, dipropylene glycol diamethcrylate, 1,12-dodecanedioldimethacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated (2)bisphenol A dimethacrylate, ethoxylated (3) bisphenol A diacrylate,ethoxylated (4) bisphenol A diacrylate, ethoxylated (4) bisphenol Adimethacrylate, ethoxylated (6) bisphenol A dimethacrylate, ethoxylated(8) bisphenol A dimethacrylate, ethoxylated (10) bisphenol A diacrylate,ethoxylated (10) bisphenol A dimethacrylate, ethoxylated (30) bisphenolA diacrylate, ethoxylated (30) bisphenol A dimethacrylate, ethyleneglycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, polyester diacrylate, polyethylene glycol (200)diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol(400) dimethacrylate, polyethylene glycol (600) diacrylate, polyethyleneglycol (600) dimethacrylate, polyethylene glycol dimethacrylate,polypropylene glycol (400) dimethacrylate, propoxylated neopentyl glycoldiacrylate, propoxylated neopentyl glycol dimethacrylate, propoxylated(2) neopentyl glycol diacrylate, tetraethylene glycol diacrylate,tetraethylene glycol dimethacrylate, tricyclodecane dimethanoldiacrylate, triethylene glycol diacrylate, triethylene glycoldimethacrylate, tripropylene glycol diacrylate and tripropylene glycoldimethacrylate and combinations thereof.

In some applications, the multifunctional monomer/oligomer istrifunctional. Examples of trifunctional monomer/oligomer that can beincluded in the resin composition include ethoxylated (3)trimethylolpropane triacrylate, ethoxylated (3) trimethylolpropanetrimethacrylate, ethoxylated (6) trimethylolpropane triacrylate,ethoxylated (9) trimethylolpropane triacrylate, ethoxylated (15)trimethylolpropane triacrylate, ethoxylated (20) trimethylolpropanetriacrylate, pentaerythritol triacrylate, propoxylated (3) glyceryltriacrylate, propoxylated (3) glyceryl triacrylate, propoxylated (5.5)glyceryl triacrylate, propoxylated (3) trimethylolpropane triacrylate,propoxylated (6) trimethylolpropane triacrylate, trimethylolpropanetriacrylate, trimethylolpropane trimethacrylate,tris-(2-hydroxyethyl)-isocyanurate triacrylate and tris-(2-hydroxyethyl)-isocyanurate trimethacrylate and combinations thereof.

In some applications, the multifunctional monomer/oligomer istetrafunctional or pentafunctional. Examples of tetrafunctional orpentafunctional monomer/oligomer that can be included in the resincomposition include di-(trimethylolpropane)-tetraacrylate, ethoxylated(4) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate,pentaacrylate ester and pentaerythritol tetraacrylate and combinationsthereof.

The ratio of different functionality monomers and oligomers can beoptimized to achieve an optimized balance between stretchability andsurface resistant properties that are required by some applications,such as for labels that are to be applied to detergent bottles, shampoobottles or gasoline bottles

B. Inks and Coatings

Provided herein are high-stretch energy curable inks and coating. Theinks and coatings demonstrate good printability, fast cure, and aftercuring stretch 25% or more without cracking when printed up to 5 layerswith multi color traps with or without first down clear coating and withor without last down white. The energy curable inks and coatings can beused in heat-transfer label (HTL) applications, e.g., in actinic energy{e.g., UV/EB) curable offset inks in multi-layer HTL applications thatrequire high stretch during the heat-transfer process. The energycurable inks and coatings provided herein, when cured to form cured inksand coatings, are resistant to abrasion, water, chemicals, and heat, andexhibit good flexibility and extensibility.

The high-stretch energy curable inks and coatings provided hereininclude a resin composition provided herein, optionally a pigment/dyeand optionally any one or more of an inhibitor, a viscosity modifier, aphotoinhibitor and an additive. For example, a non-white ink can contain40 wt % to 70 wt % resin composition provided herein and 0.1 wt % to 30wt % pigment/dye and optionally 0.1 wt % to 30 wt % viscosity modifierto adjust viscosity and/or modulate Tg. An exemplary ink formula isshown in Table 1.

TABLE 1 Exemplary Non-White Ink Formula Material Type % Resincomposition as described herein 40-70%  Inhibitor 0-3%  Viscositymodifier 0-30% Photoinitiator 0-15% Pigment/dye 0.1-30%  Additives 0-15%

A white ink composition generally contains a higher amount of whitepigment, e.g., to provide the coverage or density desired. Any whitepigment known in the art can be included in the formulation. Anexemplary white ink can contain 20 wt % to 50 wt % resin compositionprovided herein, 5 wt %> to 60 wt %> of a white pigment, and optionally0.1 wt %> to 30 wt %> viscosity modifier to adjust viscosity. Anexemplary white ink formula is shown in Table 2.

TABLE 2 Exemplary White Ink Formula Material Type % Resin solution in amonofunctional monomer 20-50%  Inhibitor 0-3%  Monofunctional monomer(to adjust viscosity) 0-30% Photoinitiators 0-15% White pigment (Such asTiO₂) 5-60% Additives 0-10%

An exemplary clear coating can contain 60 wt % to 90 wt % resincomposition provided herein, and optionally 0.1 wt %> to 20 wt %>viscosity modifier to adjust viscosity. An exemplary clear coatingformula is shown in Table 3.

TABLE 3 Exemplary Clear Coating Material Type % Resin solution in amonofunctional monomer 60-90    Inhibitor 0-3%  Monofunctional monomer(to adjust viscosity) 0-20% Photoinitiators 0-12% Additives 0-15%

1. Resin Composition in the Inks and Coatings

The high-stretch energy curable ink compositions provided hereingenerally include 40 wt % or more of the resin composition providedherein based on the total weight of the ink composition. Forhigh-stretch energy curable white ink compositions, the amount of resincomposition provided herein included in the ink generally is between 20wt % and 50 wt % based on the weight of the ink composition. Forhigh-stretch energy curable clear coating compositions, the amount ofresin composition provided herein included in the ink generally isbetween 60 wt % and 90 wt % based on the weight of the ink composition.In some applications, the resin composition is selected so that, basedon the weight of the resin, the amount of monofunctionalmonomers/oligomers in the resin composition is 70 wt % or greater andthe amount of inert resin is 20 wt % or less; or the amount ofmonofunctional monomers and/or oligomers in the resin composition is 80wt % or greater and the amount of inert resin is 20 wt % or less; or theamount of monofunctional monomers/oligomers in the resin composition is85 wt % or greater and the amount of inert resin is 15 wt % or less; orthe amount of monofunctional monomers/oligomers in the resin compositionis 90 wt % or greater and the amount of inert resin is 10 wt % or less;or the amount of monofunctional monomers/oligomers in the resincomposition is 95 wt % or greater and the amount of inert resin is 5 wt% or less based on the total weight of the resin composition. Coloredand white ink compositions of the present application preferably includea resin composition as described above containing <20 wt %, morepreferably <10 wt %, more preferably <5 wt %, most preferably 0 wt %, ofmultifunctional monomers and/or oligomers, based on the weight of theresin composition. In some applications the ink compositions and whiteink compositions exclude multifunctional monomers/oligomers. Clearcoating compositions of the present application preferably include aresin composition as described above containing up to 20 wt %, morepreferably up to 10 wt %, and more preferably up to 5 wt % ofmultifunctional monomers/oligomers, based on the weight of the resincomposition, and in some applications the clear coating compositionsexclude multifunctional monomers/oligomers.

For non-white inks, the total amount of resin composition based on theweight of the ink can be from 30 wt % to 80 wt %, and generally is 30 wt% or greater, or 35 wt % or greater, or 40 wt % or greater, or 45 wt %or greater, or 50 wt % or greater, or 55 wt % or greater, or 60 wt % orgreater, or 65 wt % or greater. In some applications, the total amountof resin composition based on the weight of the ink is in the range ofat or about 40 wt % and 70 wt %, or between at or about 45 wt % and 65wt %, or between at or about 50 wt % and 70 wt %. For some inks, thetotal amount of resin composition based on the weight of the ink is 40wt %, 40.5 wt %, 41 wt %, 41.5 wt %, 42 wt %, 42.5 wt %, 43 wt %, 43.5wt %, 44 wt %, 44.5 wt %, 45 wt %, 45.5 wt %, 46 wt %, 46.5 wt %, 47 wt%, 47.5 wt %, 48 wt %, 48.5 wt %, 49 wt %, 49.5 wt %, 50 wt %, 50.5 wt%, 51 wt %, 51.5 wt %, 52 wt %, 52.5 wt %, 53 wt %, 53.5 wt %, 54 wt %,54.5 wt %, 55 wt %, 55.5 wt %, 56 wt %, 56.5 wt %, 57 wt %, 57.5 wt %,58 wt %, 58.5 wt %, 59 wt %, 59.5 wt %, 60 wt %, 60.5 wt %, 61 wt %,61.5 wt %, 62 wt %, 62.5 wt %, 63 wt %, 63.5 wt %, 64 wt %, 64.5 wt %,65 wt %, 65.5 wt %, 66 wt %, 66.5 wt %, 67 wt %, 67.5 wt %, 68 wt %,68.5 wt %, 69 wt %, 69.5 wt %, 70 wt %, 70.5 wt %, 71 wt %, 71.5 wt %,72 wt %, 72.5 wt %, 73 wt %, 73.5 wt %, 74 wt %, 74.5 wt %, 75 wt %,75.5 wt %, 76 wt %, 76.5 wt %, 77 wt %, 77.5 wt %, 78 wt %, 78.5 wt %,79 wt %, 79.5 wt % or 80 wt %.

For white inks, the total amount of resin composition based on theweight of the ink generally is 20 wt % or greater, or 25 wt % orgreater, or 30 wt % or greater, or 35 wt % or greater, or 40 wt % orgreater, or 45 wt % or greater. In some applications, the total amountof resin composition based on the weight of the white ink is in therange of at or about 20 wt % and 50 wt %, or between at or about 25 wt %and 45 wt %, or between at or about 20 wt % and 40 wt % or between at orabout 30 wt % and 50 wt %. For some white inks, the total amount ofresin composition based on the weight of the ink is 20 wt %, 20.5 wt %,21 wt %, 21.5 wt %, 22 wt %, 22.5 wt %, 23 wt %, 23.5 wt %, 24 wt %,24.5 wt %, 25 wt %, 25.5 wt %, 26 wt %, 26.5 wt %, 27 wt %, 27.5 wt %,28 wt %, 28.5 wt %, 29 wt %, 29.5 wt %, 30 wt %, 30.5 wt %, 31 wt %,31.5 wt %, 32 wt %, 32.5 wt %, 33 wt %, 33.5 wt %, 34 wt %, 34.5 wt %,35 wt %, 35.5 wt %, 36 wt %, 36.5 wt %, 37 wt %, 37.5 wt %, 38 wt %,38.5 wt %, 39 wt %, 39.5 wt %, 40 wt %, 40.5 wt %, 41 wt %, 41.5 wt %,42 wt %, 42.5 wt %, 43 wt %, 43.5 wt %, 44 wt %, 44.5 wt %, 45 wt %,45.5 wt %, 46 wt %, 46.5 wt %, 47 wt %, 47.5 wt %, 48 wt %, 48.5 wt %,49 wt %, 49.5 wt % or 50 wt %.

For clear coatings, the total amount of resin composition based on theweight of the ink generally is 60 wt % or greater, or 65 wt % orgreater, or 70 wt % or greater, or 75 wt % or greater, or 70 wt % orgreater, or 75 wt % or greater, or 80 wt % or greater, or 85 wt % orgreater. In some applications, the total amount of resin compositionbased on the weight of the clear coating is between at or about 60 wt %and 90 wt %, or between at or about 60 wt % and 85 wt %, or between ator about 60 wt % and 80 wt %, or between at or about 60 wt % and 75 wt%, or between at or about 75 wt % and 90 wt %, or between at or about 80wt % and 90 wt %. For some clear coatings, the total amount of resincomposition based on the weight of the clear coating is 60 wt %, 60.5 wt%, 61 wt %, 61.5 wt %, 62 wt %, 62.5 wt %, 63 wt %, 63.5 wt %, 64 wt %,64.5 wt %, 65 wt %, 65.5 wt %, 66 wt %, 66.5 wt %, 67 wt %, 67.5 wt %,68 wt %, 68.5 wt %, 69 wt %, 69.5 wt %, 70 wt %, 70.5 wt %, 71 wt %,71.5 wt %, 72 wt %, 72.5 wt %, 73 wt %, 73.5 wt %, 74 wt %, 74.5 wt %,75 wt %, 75.5 wt %, 76 wt %, 76.5 wt %, 77 wt %, 77.5 wt %, 78 wt %,78.5 wt %, 79 wt %, 79.5 wt %, 80 wt %, 80.5 wt %, 81 wt %, 81.5 wt %,82 wt %, 82.5 wt %, 83 wt %, 83.5 wt %, 84 wt %, 84.5 wt %, 85 wt %,85.5 wt %, 86 wt %, 86.5 wt %, 87 wt %, 87.5 wt %, 88 wt %, 88.5 wt %,89 wt %, 89.5 wt % and 90 wt %.

2. Viscosity Modifier

The high-stretch energy curable ink, white ink and clear coatingcompositions provided herein can include a viscosity modifier tomodulate the final viscosity of the ink formulation. Any viscositymodifier known and used in the art of heat transfer labels and inks canbe included in the ink and coating formulations provided herein.Examples of viscosity modifiers that can be included in the inks andcoatings provided herein include acrylate esters, acrylic esters,acrylic monomer, aliphatic mono acrylate, aliphatic mono methacrylate,alkoxylated lauryl acrylate, alkoxylated phenol acrylate, alkoxylatedtetrahydrofurfuryl acrylate, C12-C14 alkyl methacrylate, aromaticacrylate monomer, aromatic methacrylate monomer, caprolactone acrylate,cyclic trimethylol-propane formal acrylate, cycloaliphatic acrylatemonomer, dicyclopentadienyl methacrylate, diethylene glycol methyl ethermethacrylate, epoxidized soybean fatty acid esters, epoxidized linseedfatty acid esters, epoxy acrylate, epoxy(meth)acrylate,2-(2-ethoxy-ethoxy) ethyl acrylate, ethoxylated (4) nonyl phenolacrylate, ethoxylated (4) nonyl phenol methacrylate, ethoxylated nonylphenol acrylate, hydroxy-terminated epoxidized 1,3-polybutadiene,isobornyl acrylate, isobornyl methacrylate, isodecyl acrylate, isodecylmethacrylate, isooctyl acrylate, isooctyl methacrylate, lauryl acrylate,lauryl methacrylate, methoxy polyethylene glycol (350) monoacrylate,methoxy polyethylene glycol (350) monomethacrylate, methoxypoly-ethylene glycol (550) monoacrylate, methoxy polyethylene glycol(550) mono-methacrylate, nonyl-phenyl polyoxyethylene acrylate,octyldecyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethylmethacrylate, polybutadiene polymer, polyester acrylate, polyestermethacrylate, polyether acrylate, polyether methacrylate, stearylacrylate, stearyl methacrylate, tetrahydrofurfuryl acrylate,tetrahydrofurfuryl methacrylate, triethylene glycol ethyl ethermethacrylate, 3,3,5-trimethylcyclohexyl methacrylate, urethane acrylateand urethane methacrylate and combinations thereof.

A monomer can be used to decrease the viscosity of an oligomer. Forexample, the viscosity modifier in the inks or coatings provided hereincan be a monofunctional monomer or monofunctional oligomer as describedherein as part of the resin composition or a thermoplastic resin asdescribed herein as part of the resin composition or a combination of amonofunctional monomer/oligomer and a thermoplastic resin. In someapplications, the viscosity modifier can be the same monofunctionalmonomer or monofunctional oligomer that is present in the resincomposition. In some applications, the viscosity modifier can be thesame inert resin or inert thermoplastic resin that is present in theresin composition. In some applications, the viscosity modifier is notthe same monofunctional monomer or monofunctional oligomer as is presentin the resin composition. In some applications, the viscosity modifieris not the same inert resin or inert thermoplastic resin as is presentin the resin composition.

The amount of viscosity modifier in the colored or white ink or coating,e.g., clear coating, can vary depending on the type of process used toapply the ink or coating. The viscosity ranges for the various forms ofnon-contact printing, including but not limited to, continuous anddrop-on-demand ink jet, and for suitable forms of contact printing,including, but not limited to, gravure and lithographic printing andflexography, are well known to those skilled in the art of printing. Forexample, see The Printing Ink Manual (5th ed., Leach et al. eds. (2009),pages 549-551 and 554-555 for flexographic printing; pages 485-489 forgravure printing; pages 682, 683, 696 and 697 for inkjet printing; pages348 and 381 for lithographic printing).

For example, inks used with lithographic (e.g., offset) printingtypically need to have a viscosity of at least at or about 4,500 cP(Brookfield HBDV-E viscometer at 25° C.), and the viscosity can be inthe range of 5,000 cP to 15,000 cP, and in some applications, can have aviscosity in the range of 6,000 cP to 12,000 cP, and in someapplications, can have a viscosity of at least about 10,000 cP, or atleast about 14,000 cP. Inks formulated for flexographic printinggenerally have a lower viscosity, typically a viscosity of at less thanabout 2,000 cP, and in some applications can be formulated to have aviscosity of less than at or about 1,000 cP or less than at or about 500cP. Inks formulated for gravure printing generally are formulated tohave a viscosity between 15 and 25 seconds (Zahn Cup No. 2 at 25° C.).

Thus, for a given ink or coating containing a resin (which includes amixture of monofunctional monomer/oligomer, inert resin and 0-20%multifunctional monomer or oligomer) and other components {e.g.,pigment/dye, photoinitiator, additives, discussed below), a greateramount of viscosity modifier may be needed for flexographic, gravure andother types of printing (to reduce the viscosity), while less viscositymodifier may be needed for lithographic {e.g., offset) printing. Theamount of viscosity modifier that can be included in the inkformulations can vary depending on the type of process used to apply theink. In some applications, the amount of viscosity modifier based on theweight of the ink composition is between at or about 0.1 wt % to at orabout 30 wt %. In some applications, the amount of viscosity modifierbased on the weight of the ink composition is in the range of 1 wt % to25 wt %, or 5 wt % to 20 wt %, or 5 wt % to 15 wt %, or 0.1 wt % to 10wt %, or 0.5 wt % to 5 wt %. In some applications, the amount ofviscosity modifier present in the ink is 0.1%, 0.2 wt %, 0.3 wt %, 0.4wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %, 1.25 wt%, 1.5 wt %, 1.75 wt %, 2 wt %, 2.25 wt %, 2.5 wt %, 2.75 wt %, 3 wt %,3.25 wt %, 3.5 wt %, 3.75 wt %, 4 wt %, 4.25 wt %, 4.5 wt %, 4.75 wt %,5%, 5.25 wt %, 5.5%, 5.75 wt %, 6 wt %, 6.25 wt %, 6.5 wt %, 6.75 wt %,7 wt %, 7.25 wt %, 7.5 wt %, 7.75 wt %, 8 wt %, 8.25 wt %, 8.5 wt %,8.75 wt %, 9 wt %, 9.25 wt %, 9.5 wt %, 9.75 wt %, 10 wt %, 11 wt %,11.25 wt %, 11.5 wt %, 11.75 wt %, 12 wt %, 12.25 wt %, 12.5 wt %, 12.75wt %, 13 wt %, 13.25 wt %, 13.5 wt %, 13.75 wt %, 14 wt %, 14.25 wt %,14.5 wt %, 14.75 wt %, 15%, 15.25 wt %, 15.5%, 15.75 wt %, 16 wt %,16.25 wt %, 16.5 wt %, 16.75 wt %, 17 wt %, 17.25 wt %, 17.5 wt %, 17.75wt %, 18 wt %, 18.25 wt %, 18.5 wt %, 18.75 wt %, 19 wt %, 19.25 wt %,19.5 wt %, 19.75 wt %, 20 wt %, 21.25 wt %, 21.5 wt %, 21.75 wt %, 22 wt%, 22.25 wt %, 22.5 wt %, 22.75 wt %, 23 wt %, 23.25 wt %, 23.5 wt %,23.75 wt %, 24 wt %, 24.25 wt %, 24.5 wt %, 24.75 wt %, 25%, 25.25 wt %,25.5%, 25.75 wt %, 26 wt %, 26.25 wt %, 26.5 wt %, 26.75 wt %, 27 wt %,27.25 wt %, 27.5 wt %, 27.75 wt %, 28 wt %, 28.25 wt %, 28.5 wt %, 28.75wt %, 29 wt %, 29.25 wt %, 29.5 wt %, 29.75 wt % or 30 wt %, based onthe weight of the ink composition.

The Tg or viscosity or both of the inert resin can be modulated by thepresence of monofunctional monomers/oligomers. For example, one or moreor a combination of monofunctional monomers/oligomers can be used as aviscosity modifying agent to reduce the apparent viscosity of the resincompositions provided herein containing a high viscosity inert resin. Asthe amount of monofunctional monomers/oligomers in the resin compositionincreases, the apparent viscosity of the resin composition decreases.

Similarly, including monofunctional monomers/oligomers in the resincomposition can result in an observed decrease in Tg of an otherwiseunworkable inert resin due to its high Tg when not in the presence ofmonofunctional monomers/oligomers.

3. Photoinitiator

The high-stretch energy curable inks of the present application cancontain one or more photoinitiators. Examples of photoinitiators thatcan be included in the ink compositions include, but are not limited to,benzoin ethers, such as benzoin methyl ether, benzoin ethyl ether, andbenzoin phenyl ether; alkylbenzoins, such as methylbenzoin,ethylbenzoin, propylbenzoin, butylbenzoin and pentylbenzoin; benzylderivatives, such as benzyl-dimethylketal; 2,4,5-triaryl-imidazoledimers, such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer,2-(o-chloro-phenyl)-4,5-di(m-methoxyphenyl)imidazole dimer,2-(o-fluorophenyl)-4,5-phenyl-imidazole dimer,2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dimer,2-(p-methoxy-phenyl)-4,5-diphenylimidazole dimer,2,4-di(p-methoxy-phenyl)-5-phenyl-imidazole dimer and2-(2,4-dimethoxyphenyl)-4,5-diphenyl-imidazole dimer; acridinederivatives such as 9-phenylacridine and 1,7-bis(9,9′-aridinyl)heptane;N-phenylglycine; benzophenones, anthraquinones, thioxanthones andderivatives thereof, including chloro-benzophenone,4-phenylbenzophenone, trimethyl-benzophenone,3,3′-dimethyl-4-methoxybenzophenone, 4,4′-dimethylamino-benzophenone,4,4′-bis(diethyl-amino)-benzophenone, acrylated benzophenone,methyl-o-benzoyl benzoate, isopropyl-thioxanthone, 2-chloro and2-ethyl-thioxanthone,2-benzyl-2-(dimethyl-amino)-4′-morpholino-butyrophenone and hydroxybenzophenone; acetophenone derivatives including2,2-dimethoxy-2-phenyl-acetophenone, 2,2-diethoxyacetophenone,2,2-dimethoxy-2-phenylacetophene and 1-hydroxycyclohexylacetophenone;2-hydroxy-2-methyl-1-phenylpropanone; 4-benzoyl-4′-methyl-diphenylsulfide; ethyl 4-dimethyl-amino-benzoate; 2-ethyl-hydroquinone;(2,4,6-trimethylbenzoyl)diphenyl phosphine oxide (Lucerin TPO, availablefrom BASF, Munich, Germany); ethyl(2,4,6-trimethyl-benzoyl-phenylphosphinate; a-hydroxy ketone photoinitiators, such as1-hydroxy-cyclohexyl-phenyl ketone (e.g., Irgacure® 184 available fromCiba Specialty Chemical (Hawthorne, N.Y.),2-hydroxy-2-methyl-1-phenylpropanone,2-hydroxy-2-methyl-1-(4-isopropylphenyl)propanone,2-hydroxy-2-methyl-1-(4-dodecylphenyl)propanone,2-hydroxy-2-methyl-1-phenylpropanone and2-hydroxy-2-methyl-1-[(2-hydroxyethoxy)-phenyljpropanone;(2,6-dimethoxy-benzoyl)-2,4,4-trimethylpentyl phosphine oxide (e.g.,commercial blends Irgacure® 1800, 1850, and 1700 available from CibaSpecialty Chemical); 2,2-dimethoxyl-2-phenyl acetophenone (e.g.,Irgacure® 651, available from Ciba Specialty Chemical); bisacylphosphineoxide photoinitiators, such asbis(2,4,6-trimethylbenzoyl)phenyl-phosphine oxide (e.g., Irgacure® 819from Ciba Specialty Chemical),bis(2,6-dimethoxybenzoyl)-isooctyl-phosphine oxide andethoxy(2,4,6-trimethyl-benzoyl) phenyl phosphine oxide (Lucerin® TPO-Lfrom BASF), and combinations thereof.

The amount of photoinitiator present in the ink generally is 15 wt % orless based on the weight of the ink composition. In some applications,the amount of photoinitiator present in the ink generally is 10 wt % orless, or 5 wt % or less, based on the weight of the ink composition. Insome applications, the amount of photoinitiator present in the ink is0.1%, 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt%, 0.9 wt %, 1 wt %, 1.25 wt %, 1.5 wt %, 1.75 wt %, 2 wt %, 2.25 wt %,2.5 wt %, 2.75 wt %, 3 wt %, 3.25 wt %, 3.5 wt %, 3.75 wt %, 4 wt %,4.25 wt %, 4.5 wt %, 4.75 wt %, 5%, 5.25 wt %, 5.5%, 5.75 wt %, 6 wt %,6.25 wt %, 6.5 wt %, 6.75 wt %, 7 wt %, 7.25 wt %, 7.5 wt %, 7.75 wt %,8 wt %, 8.25 wt %, 8.5 wt %, 8.75 wt %, 9 wt %, 9.25 wt %, 9.5 wt %,9.75 wt %, 10 wt %, 11 wt %, 11.25 wt %, 11.5 wt %, 11.75 wt %, 12 wt %,12.25 wt %, 12.5 wt %, 12.75 wt %, 13 wt %, 13.25 wt %, 13.5 wt %, 13.75wt %, 14 wt %, 14.25 wt %, 14.5 wt %, 14.75 wt % or 15%.

4. Pigment/Dye

The high-stretch energy curable inks and coatings provided herein caninclude a colorant, such as a pigment or dye or combination thereof. Anyorganic and/or inorganic pigments and dyes can be included in the inks.Exemplary pigments suitable for use in the present invention includeInternational Color Index or C.I. Pigment Black Numbers 1, 7, 11 and 31,C.I. Pigment Blue Numbers 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 27, 29,61 and 62, C.I. Pigment Green Numbers 7, 17, 18 and 36, C.I. PigmentOrange Numbers 5, 13, 16, 34 and 36, C.I. Pigment Violet Numbers 3, 19,23 and 27, C.I. Pigment Red Numbers 3, 17, 22, 23, 48:1, 48:2, 57:1,81:1, 81:2, 81:3, 81:5, 101, 114, 122, 144, 146, 170, 176, 179, 181,185, 188, 202, 206, 207, 210 and 249, C.I. Pigment Yellow Numbers 1, 2,3, 12, 13, 14, 17, 42, 65, 73, 74, 75, 83, 93, 109, 110, 128, 138, 139,147, 142, 151, 154 and 180, D&C Red No. 7, D&C Red No. 6 and D&C Red No.34, carbon black pigment (such as Regal 330, Cabot Corporation),quinacridone pigments (Quinacridone Magenta (228-0122), available fromSun Chemical Corporation, Fort Lee, N.J.), diarylide yellow pigment(such as AAOT Yellow (274-1788) available from Sun ChemicalCorporation); and phthalocyanine blue pigment (such as Blue 15:3(294-1298) available from Sun Chemical Corporation). The classes of dyessuitable for use in present invention can be selected from acid dyes,natural dyes, direct dyes (either cationic or anionic), basic dyes, andreactive dyes. The acid dyes, also regarded as anionic dyes, are solublein water and mainly insoluble in organic solvents and are selected, fromyellow acid dyes, orange acid dyes, red acid dyes, violet acid dyes,blue acid dyes, green acid dyes, and black acid dyes. European Patent0745651, incorporated herein by reference, describes a number of aciddyes that are suitable for use in the present invention. Exemplaryyellow acid dyes include Acid Yellow 1 International Color Index or C.I.10316); Acid Yellow 7 (C.I. 56295); Acid Yellow 17 (C.I. 18965); AcidYellow 23 (C.I. 19140); Acid Yellow 29 (C.I. 18900); Acid Yellow 36(C.I. 13065); Acid Yellow 42 (C.I. 22910); Acid Yellow 73 (C.I. 45350);Acid Yellow 99 (C.I. 13908); Acid Yellow 194; and Food Yellow 3 (C.I.15985). Exemplary orange acid dyes include Acid Orange 1 (C.I. 13090/1);Acid Orange 10 (C.I. 16230); Acid Orange 20 (C.I. 14603); Acid Orange 76(C.I. 18870); Acid Orange 142; Food Orange 2 (C.I. 15980); and Orange B.Exemplary red acid dyes include Acid Red 1. (C.I. 18050); Acid Red 4(C.I. 14710); Acid Red 18 (C.I. 16255), Acid Red 26 (C.I. 16150); AcidRed 2.7 (C.I. as Acid Red 51 (C.I. 45430, available from BASFCorporation, Mt. Olive, N.J.) Acid Red 52 (C.I. 45100); Acid Red 73(C.I. 27290); Acid Red 87 (C. I. 45380); Acid Red 94 (C.I. 45440) AcidRed 194; and Food Red 1 (C.I. 14700). Exemplary violet acid dyes includeAcid Violet 7 (C.I. 18055); and Acid Violet 49 (C.I. 42640). Exemplaryblue acid dyes include Acid Blue 1 (C.I. 42045); Acid Blue 9 (C.I.42090); Acid Blue 22 (C.I. 42755); Acid Blue 74 (C.I. 73015); Acid Blue93 (C.I. 42780); and Acid Blue 158A (C.I. 15050). Exemplary green aciddyes include Acid Green 1 (C.I. 10028); Acid Green 3 (C.I. 42085); AcidGreen 5 (C.I. 42095); Acid Green 26 (C.I. 44025); and Food Green 3 (C.I.42053). Exemplary black acid dyes include Acid Black 1 (C.I. 20470);Acid Black 194 (Basantol® X80, available from BASF Corporation, anazo/1:2 CR-complex.

Exemplary direct dyes for use in the present invention include DirectBlue 86 (C.I. 74180); Direct Blue 199; Direct Black 168; Direct Red 253;and Direct Yellow 107/132 (C.I. Not Assigned).

Exemplary natural dyes for use in the present invention include Alkanet(C.I. 75520, 75530); Annafto (C.I. 75120); Carotene (C.I. 75130);Chestnut; Cochineal (C.I. 75470); Cutch (C.I. 75250, 75260); Divi-Divi;Fustic (C.I. 75240); Hypernic (C.I. 75280); Logwood (C.I. 75200); OsageOrange (C.I. 75660); Paprika; Quercitron (C.I. 75720); Sanrou (C.I.75100); Sandal Wood (C.I. 75510, 75540, 75550, 75560); Sumac; andTumeric (C.I. 75300). Exemplary reactive dyes for use in the presentinvention include Reactive Yellow 37 (monoazo dye); Reactive Black 31(disazo dye); Reactive Blue 77 (phthalo cyanine dye) and Reactive Red180 and Reactive Red 108 dyes. Suitable also are the colorants describedin The Printing Ink Manual (5th ed., Leach et al. eds. (2007), pages289-299. Other organic and inorganic pigments and dyes and combinationsthereof can be used to achieve the colors desired.

In addition to or in place of visible colorants, the high stretch inksand coatings provided herein composition can contain UV fluorophoresthat are excited in the UV range and emit light at a higher wavelength(typically 400 nm and above). Examples of UV fluorophores include butare not limited to materials from the coumarin, benzoxazole, rhodamine,napthalimide, perylene, benzanthrones, benzoxanthones orbenzothia-xanthones families. The addition of a UV fluorophore (such asan optical brightener for instance) can help maintain maximum visiblelight transmission. The amount of colorant, when present, generally isbetween 0.05% to 5% or between 0.1% and 1% based on the weight of theink or coating composition.

For non-white inks, the amount of pigment/dye generally is present in anamount of from at or about 0.1 wt % to at or about 20 wt % based on theweight of the ink composition. In some applications, a non-white ink caninclude 15 wt % or less pigment/dye, or 10 wt % or less pigment/dye or 5wt % pigment/dye, or 1 wt % pigment/dye based on the weight of the inkcomposition. In some applications, a non-white ink can include 1 wt % to10 wt %, or 5 wt % to 15 wt %, or 10 wt % to 20 wt % pigment/dye basedon the weight of the ink composition. In some applications, a non-whiteink can contain an amount of dye/pigment that is 1 wt %, 2 wt %, 3 wt %,4 wt %, 5%, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %,13 wt %, 14 wt %, 15%, 16 wt %, 17 wt %, 18 wt %, 19 wt % or 20 wt %based on the weight of the ink composition.

For white ink compositions, the amount of white pigment generally ispresent in an amount of from at or about 1 wt % to at or about 60 wt %based on the weight of the ink composition. In some applications,greater than 60 wt % white pigment can be present. Preferred whitepigments include titanium dioxide (anatase and rutile), zinc oxide,lithopone (calcined coprecipitate of barium sulfate and zinc sulfide),zinc sulfide, blanc fixe and alumina hydrate and combinations thereof,although any of these can be combined with calcium carbonate. In someapplications, a white ink can include 60 wt % or less white pigment, or55 wt % or less white pigment, or 50 wt % white pigment, or 45 wt %white pigment, or 40 wt % white pigment, or 35 wt % white pigment, or 30wt % white pigment, or 25 wt % white pigment, or 20 wt % white pigment,or 15 wt % white pigment, or 10 wt % white pigment, based on the weightof the ink composition. In some applications, a white ink can include 5wt % to 60 wt %, or 5 wt % to 55 wt %, or 10 wt % to 50 wt %, or 10 wt %to 25 wt %, or 25 wt % to 50 wt %, or 5 wt % to 15 wt %, or 40 wt % to60 wt % white pigment based on the weight of the ink composition. Insome applications, a non-white ink can an amount of dye/pigment that is5%, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %,14 wt %, 15%, 16 wt %, 17 wt %, 18 wt %, 19 wt %, 20 wt %, 21 wt %, 22wt %, 23 wt %, 24 wt %, 25%, 26 wt %, 27 wt %, 28 wt %, 29 wt %, 30 wt%, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35%, 36 wt %, 37 wt %, 38 wt %,39 wt %, 40 wt %, 41 wt %, 42 wt %, 43 wt %, 44 wt %, 45%, 46 wt %, 47wt %, 48 wt %, 49 wt %, 50 wt %, 51 wt %, 52 wt %, 53 wt %, 54 wt %,55%, 56 wt %, 57 wt %, 58 wt %, 59 wt % or 60 wt % based on the weightof the ink composition.

For clear coatings, colorants such as optical brighteners can beincluded. In some applications, no colorant, pigment or dye is includedin the clear coatings. When present, the amount of colorant, pigment ordye generally is 10 wt % or less based on the weight of the inkcomposition.

5. Additives

The ink, white ink and clear coating compositions can include one ormore of various additives, such as, e.g., ammonia, anti-misting agents{e.g., silica and microtalc), clay, defoamers, dispersants, flow agents,inhibitors, lubricants {e.g., wax), plasticizers, silicones,stabilizers, talc, wetting agents, or any combination thereof. Each ofthese additives can be used in an ink or coating of this disclosure at alevel of from about 0.001% to about 10% or more based on the weight ofthe ink composition.

Wetting agents can be included in the inks or coatings, e.g., to modifysurface tension. Exemplary wetting agents include polyether modifiedpolydimethylsiloxane (BYK®307), xylene, ethylbenzene, a blend of xyleneand ethylbenzene (BYK0310), octamethylcyclo-tetrasiloxane (BYK0331) andalcohol alkoxylates {e.g., BYK® DYNWET). Any foam destroying or foammitigating polymer or compound can be included in the inks as adefoamer. Examples of these include polysiloxanes, oxyalkylene amines,silicone oils and fluids, polyacrylates, polyglycol, polyols, andpolyether modified methylalkyl polysiloxane copolymers and combinationsthereof.

In some applications, the inks or coatings can include one or morepolymerization inhibitors or stabilizers for radically curable inks orboth. Examples of these include benzoquinone, benzotriazolealuminiumsalt amine complexes, butylated hydroxytoluene, hydroquinone,hydroquinone monomethyl ether, Florstab® UV-1 (Kromachem LTD), Genorad®16 inhibitor compound (Rahn Corporation), Irgastab® UV-10 and Irgastab®UV-22 (Ciba Specialty Chemicals Inc.), naphthoquinone, t-butylcatechol,t-butylhydroquinone and combinations thereof.

The inks or coatings can a flow agent. Examples of flow agents that canbe included in the inks or coatings include, e.g., butyrates,celluloses, polyacrylates, surfactants, silicones and waxes. Examples ofsurfactants include siloxanes, polyalkyleneoxide siloxanes,polyalkyleneoxide polydimethylsiloxanes, polyesterpolydimethylsiloxanes, ethoxylated nonylphenols, nonylphenoxypolyethyleneoxy-ethanol, fluorocarbon esters, fluoroaliphatic polymericesters, fluorinated esters, alkylphenoxy alkyleneoxides, cetyl trimethylammonium chloride, carboxymethyl-amylose, ethoxylated acetylene glycols,betaines, N-dodecyl-N,N-dimethylbetaine, dialkyl sulfosuccinate salts,alkylnaphthalene-sulfonate salts, fatty acid salts, polyoxyethylenealkylethers, polyoxyethylene alkylallyl-ethers,polyoxyethylene-polyoxypropylene block copolymers, alkylamine salts,quaternary ammonium salts, and mixtures thereof.

The inks or coatings can include a plasticizer. Examples of plasticizersinclude alkyl benzyl phthalates, butyl benzyl phthalates,di-2-ethylhexy-adipates, diethyl phthalates, dimethyl phthalates,dioctyl phthalates, diisobutyl phthalates, dicyclohexyl phthalates,diisobutyl adipates, glycerol tribenzoates, polypropylene glycoldibenzoates, neopentyl glycol dibenzoates, dimethyl isophthalates,dibutyl phthalates, dibutyl sebacates, sucrose benzoates,tri-n-hexyltrimellitates, and mixtures thereof.

The inks or coatings can include one or more dispersant. Examples of adispersant include acrylic block copolymers, acrylate block copolymers,graft polymers, hydrophilic-hydrophobic block copolymers, a polymerdispersant, a surfactant, and mixtures thereof.

C. Stretchability

As discussed above, the high-stretch energy curable inks and coatingsprovided herein when cured to form cured inks and cured coatings,exhibit a stretchability, such as when at least a part of a heattransfer label is stretched at least about 10%, e.g., from about 10%) toabout 30% o, or from 15% to 25%, or 25% or more, without visuallycracking. The cured inks or coatings can be stretched in any or alldirections, and generally stretched in at least one direction. In someapplications, the cured high-stretch energy curable inks and coatingsprovided herein exhibit a stretchability without cracking of 15%, 16%,17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28% 29% or 30% ormore. By virtue of this high stretchability of the inks and coatingsprovided herein, heat transfer labels containing the high-stretch energycurable inks and coating provided herein can be applied to containersthat are tapered or contoured without cracking of the label ordecoration. Commercially available UV curable coatings and inkstypically stretch only about 1-3% before cracking, and are not suitablefor modern containers that include non-cylindrical shapes or contours.Such inks often contain high strength materials that are brittle or arecrosslinked to such an extent to provide strength that they are notsufficiently elastic to elongate. The cured high-stretch energy curableinks and coatings provided herein exhibit high elongation withoutcracking and are well suited for modern non-cylindrical or contouredcontainers. The high-stretch energy curable inks and coatings providedherein also can be used in applications requiring no stretch, such aswhen the heat transfer label is to be applied to a perfectly cylindricalcontainer. The high-stretch energy curable inks and coatings providedwhen cured to form cured inks and cured coatings herein exhibit stretchof 25% or more without cracking during a heat label transfer process.

It will be appreciated that while the high-stretch energy curable inksand coating compositions and label and decorations containing the inksand coatings are described herein for use in heat transfer labelapplications, the ink and coating compositions provided herein also canbe used in other applications.

D. Exemplary High Stretch Inks and Coatings

The high stretch inks and coatings provided herein can be clear ortransparent or colorless or translucent or pearlescent or can include apigment or dye or combination thereof to have a selected color. Providedare energy curable non-white inks that include at or about 0.1 wt % toat or about 20 wt % pigment/dye and at or about 40 wt % to at or about70 wt % of a resin composition as described herein (e.g., that includesa multifunctional monomer or a multifunctional oligomer or both in anamount from 0% to at or about 20% based on the weight of thecomposition; and a combination that includes an inert resin and a monofunctional monomer or a monofunctional oligomer or both a monofunctionalmonomer and a monofunctional oligomer, where the combination is presentin an amount that is 80% or more based on the weight of thecomposition). Also provided are cured non-white inks that include at orabout 0.1 wt % to at or about 20 wt % pigment/dye and at or about 40 wt% to at or about 70 wt % of a resin composition as described herein,where the cured non-white ink exhibits stretch of 25% or more withoutcracking.

Also provided are energy curable clear coat that include at or about 60wt % to at or about 90 wt % of a resin composition described hereinbased on the weight of the ink composition. Also provided are curedclear coat compositions that include at or about 60 wt %> to at or about90 wt %> of a resin composition described herein based on the weight ofthe ink composition, where the cured clear coat exhibits stretch of 25%or more without cracking.

Also provided are energy curable white inks that include at or about 5wt % to at or about 60 wt % white pigment/dye and at or about 20 wt % toat or about 50 wt % of a resin composition described herein based on theweight of the ink composition. Also provided are cured white inks thatinclude at or about 5 wt % to at or about 60 wt % white pigment/dye andat or about 20 wt % to at or about 50 wt % of a resin compositiondescribed herein based on the weight of the ink composition, where thecured white ink when cured exhibits stretch of 25% or more withoutcracking.

E. Heat Transfer Label Applications

The inks of present application can be used to provide multilayer heattransfer labels. The multiple layer construction is not limited to anyspecific number of layers or order of application. In a preferredembodiment, the multilayer construct would contain (a) a first downclear coat; (b) 4-color process colors and/or spot colors; and (c)optionally a last down white. A layer of adhesive also can be included.

A heat transfer label for application to an article, such as acontainer, can include a carrier web, a release coat applied to thecarrier web, and a label or decoration including a high-stretch energycurable ink provided herein applied to the carrier web, the ink beingcured by application of actinic radiation, such as UV or EB, prior totransfer to the article.

In some applications, a heat transfer label can include a supportportion, such as a carrier web or other support, and a transfer portionon the support portion for transfer of the transfer portion from thesupport portion to an article upon application of heat to the supportportion while the transfer portion is placed into contact with thearticle, where the transfer portion includes one or more than one inklayers containing a high-stretch energy curable ink or coating providedherein and an adhesive layer over the outermost ink layer.

Also provided herein are thermoplastic heat transfer labels curable byexposure to actinic radiation, such as UV or EB radiation or acombinations thereof, for labeling or decorating a substrate, such as acontainer, upon application of heat and pressure while the label andsubstrate are in contact. The label can include one or more of thehigh-stretch energy-curable inks or coatings provided herein printed ona carrier, cured by exposure to actinic radiation, and the label isapplied to the substrate. The inks and coatings provided herein can beapplied to a substrate or carrier to form an ink label or decoration.The inks and/or coatings can be applied to the substrate or carrierusing any suitable process, for example, by lithographic, flexographicor gravure printing. Different printing techniques or combinationsthereof can be used to achieve the desired print quality and coatweight.

In some applications, the heat transfer label includes one or more ofthe high-stretch energy-curable inks or coatings provided herein and anadhesive. The heat transfer label also can include a release layer. Insome applications, the heat transfer label can include a high-stretchenergy-curable ink or coating provided herein, an adhesive, an imagesupport and a protective layer. The protective layer can serve as abarrier over the label to protect it from the environment, such as fromdirect physical contact that could lead to abrasion of the label. Insome applications, the release layer can serve as a protective layer forthe ink label or decoration. The protective layer can be adhereddirectly to the ink layer on one surface and adhered directly to theimage support on its opposite surface. Alternatively, a wax releaselayer can be present between the image support and the protective layer.The wax release layer can include one or a combination of waxes.

The protective layer when present can have a thickness of at or about0.5 to 50 microns, such as from 1 to 10 microns. The protective layercan include a water-based or solvent-based resin to provide abrasionresistance to the underlying label, image or decoration when dried.Exemplary solvent-based resins include phenoxy resins, polyester resinsand polyurethane resins. The protective layer can be formulated toadhere to the ink layer. In some applications, an adhesion promoter,such as a polymeric aliphatic isocyanate adhesion promoter (e.g., NB 80,Nazdar Ink, Shawnee, Kans.), can be included in the protective layer.The protective layer also can include a wax to improve scuff resistance.The protective layer also can be or include a lacquer. For examples ofprotective layers that can be included over the heat transfer labelcontaining a high-stretch energy-curable ink or coating provided herein,see U.S. Pat. Nos. 4,426,422; 5,800,656; 6,033,763; 6,083,620;6,099,944; and 6,254,970. The protective layer generally is clear oroptically transparent, although in some applications a frosted ortranslucent effect can be provided. The adhesive layer or the protectivelayer or their combination can hold the label or design together as thelabel or design is transferred to the container or substrate to belabelled or decorated.

The adhesive in the adhesive layer can include any suitable adhesive,and can be selected based on the substrate to which the label or designis to be applied and the application method to be used. Exemplaryadhesives include a heat-activatable, polyester-based adhesive,heat-activatable thermoplastic polyamide adhesive, water-based acrylicadhesives (see, e.g., U.S. Pat. No. 6,042,931), and phenoxy adhesives(e.g., U.S. Pat. No. 6,083,620). The adhesive generally softens or meltsat the temperature of application and thus stretchability of theadhesive layer generally is not a concern. In some applications, theadhesive can be selected or formulated so that the adhesive extends orelongates under the conditions of application of a HTL to an articlesufficiently so that the adhesive layer not interfere with the stretchof the HTL.

In the examples below, a clear coat was first applied on a carrier, thereleasing layer of a wax coated paper, using a Little Joe® offsetproving press (Little Joe® Color Swatcher, Inc., Belle Mead, N.J.) andthen cured by UV light under a 200 watt Hg lamp at 150 feet per minute(FPM).

Subsequently, 1-3 layers of an ink, such as a cyan ink, were applied tothe cured clear coat using a Little Joe® either with an inter curingstation (e.g., UV curing) or wet-on-wet without an inter curing station(e.g., UV cured in one step at the end).

Subsequently, a layer of white ink was applied to the cured cyan inklayers and cured by UV light under 200 watt Hg lamp at 150 FPM. Then aheat activated adhesive coating was applied to the cured ink layer. Heatactivated adhesives are known in the art (e.g., see U.S. Pat. No.4,548,857). Examples of UV cured heat activated adhesive includeJRX-1253 (commercially available from Dyna-Tech Adhesives and Coatings,Inc., of Grafton, West Va.) and Hydro Heat Seal Adhesive 7MXWF3278 (awater-based heat activated adhesive available from Color ResolutionsInternational, Fairfield, Ohio). The adhesive coating can be allowed todry at room temperature for several hours until tack free, and then theprint is ready to be tested on a heat transfer decoration machine.

The adhesive coating usually contains an adhesive material that canadhere the ink label or decoration to the container and the type ofadhesive included in the adhesive coating can vary depending on the typeof container or article to which the label or decoration is to beaffixed. For example, a suitable adhesive can contain a polyamideadhesive when the substrate to be labeled or decorated is polyethylene,while suitable adhesive for a glass substrate can contain a polyesteradhesive. In some applications, the adhesive coating can be omitted.

The amount of adhesive applied to the label or decoration can varydepending on the application. The adhesive can be applied in an amountof from about 0.25 to about 5 lb/ream (dry), for example, from 0.5 to 3lb/ream or about 1 to about 1.5 lb/ream. In some applications, theadhesive is applied in register with the ink or it can extend beyond theperipheral margin of the ink of the label or decoration. The adhesivecan be applied to the ink label or decoration using any suitableprocess, for example, by lithographic, flexographic or gravure printing.

In a preferred embodiment, the resins used in the clear coat are mainlymonofunctional acrylate/methacrylate monomers/oligomers and inertresins. The clear coat also optionally can contain some (preferably<20%, more preferably <10%) difunctional and multifunctionalacrylate/methacrylate monomers/oligomers to help improve crosslinkdensity and resistance properties. The ratio of different functionalitymonomers and oligomers can be optimized to achieve a balance betweenstretchability and surface resistant properties, such as solventresistance and scratch resistance.

The resin compositions used in the process color inks, spot color inksand white inks of the present application include a combination ofmonofunctional monomers and/or oligomers and/or inert resins thatprovide good stretchability. For example, the resin compositions can bebased mainly on monofunctional (meth)acrylate monomer and/or oligomersand inert resins. Preferably, these inks contain very limited amounts ofmultifunctional acrylic monomer/oligomers (preferably <5%, morepreferably <1%) or none at all in order to optimize stretchability andflexibility. In some applications, multifunctional monomers and/oroligomers are excluded from the inks.

The high-stretch energy curable inks and coating provided herein can beused to form a heat transfer label for application to an item, where thelabel includes a substrate, such as carrier web, an optional releaselayer applied to the substrate, and a label or decoration compositionincluding the high-stretch energy curable ink and/or coating applied tothe release layer. In use, the ink or coating on the label or decorationcomposition is cured using actinic radiation and then is transferred tothe item using a heat transfer process, such as hot stamping or theapplication of heat and pressure while the label and item are incontact.

The label or decoration composition can contain one or a plurality oflayers of high-stretch energy curable inks and coating provided herein.The thickness of each printed layer of the ink or coating may vary andmay be adjusted to achieve, e.g., a specific thickness or color density.When flexographic or lithographic/offset printing is used to form thelabel or decoration, each layer can be between 0.5 to 5 microns thick;such as 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μmor 5 μm thick. In some applications, the ink/coating layers are between1 to 2 microns. The total thickness of the inks and/or coatings that areincluded in the label or decoration composition can vary depending onthe desired color density, the technique used to apply the ink and/orcoating, and the number of layers of ink/coating that the label ordecoration contains. Because the energy curable inks/coatingcompositions provided herein can be formulated to 100% solids withoutVOCs, the dry film thickness and the wet film thickness of theinks/coatings could be about the same. Provided are high stretch heattransfer label that include at least one layer of the high stretchenergy curable inks or coatings provided herein, where the labelexhibits at least 20% stretch without cracking. In some applications,the label exhibits 25% stretch or more without cracking. In someapplications, the label includes a support portion and a transferportion. The transfer portion can include one or more layers of the highstretch inks or coatings provided herein. The high stretch heat transferlabels also can include a release layer, such as to enhance release ofthe label/design/decoration created by the one or more layers of theinks/coatings from the support portion to the article to be labeled ordecorated. The high stretch heat transfer labels also can include anadhesive layer, such as to improve adhesion of thelabel/design/decoration to the article.

1. Substrates

The energy curable inks and coatings provided herein can be printed ondifferent substrates. The substrates generally are of a flexiblematerial, such as a flexible polymer film or paper, such as wax paper ornon-wax substrates. The paper can be a label release grade or otherpolymer coated paper, as is known in the art (e.g., see U.S. Pat. No.6,939,576). The substrate also can be or include a non-silicone releaselayer. The substrate also can be a plastic or polymer film, such as anyone of an acrylic-based film, a polyamide-based film, a polyester-basedfilm, a polyolefin-based film such as polyethylene and polypropylene, apolyethylene naphthylene-based film, a polyethylene terephthalate-basedfilm, a polyurethane-based film or a PVC-based film, or a combinationthereof. In some applications, the substrate is selected to be a clearplastic or polymer film, which allows one to inspect the quality of theprinted label or decoration by viewing the printed label or decorationthrough the substrate (allowing viewing of the printed label ordecoration as it will appear on the labeled article), instead of lookingat the printed label or decoration through an adhesive layer of thelabel.

2. Release Layer

The release layer can include any suitable compound or composition thatfacilitates the release of the heat transfer label from the carrier.Exemplary components of a release layer include a polyolefin, an olefin,an undecanoic acid copolymer, and a wax, such as beeswax, candelillawax, a carnauba wax, a Fischer-Tropsch wax, a hydrocarbon wax,hydrogenated castor oil, montan wax, an oxidized wax, paraffin wax, apetroleum wax, or combinations thereof, where the waxes may bemicronized waxes. The release layer can be applied using any methodknown in the art. For example, the release layer can be applied using aprint unit or printer, such as a lithographic, flexographic, gravure ordigital print unit or printer.

When heat is applied to the label, the release layer can facilitatetransfer of the ink label or decoration to be transferred to thearticle. The release layer can be formulated to include ingredients thatsoften and/or become molten when heated, facilitating transfer of theink label or decoration. When formulated to soften or melt at thetemperature of application, stretchability of the release layergenerally is not a concern. In some applications, the release layer canbe selected or formulated so that the release layer extends or elongatesunder the conditions of application of a HTL to an article sufficientlyso that the release layer not interfere with the stretch of the HTL. Therelease layer can serve as a protective layer for the ink label ordecoration. The amount of release layer included can vary byapplication. The amount of release layer applied to the ink label ordecoration can be up to at or about 5 lb/ream, such as from at or about0.25 to at or about 5 lb/ream on a dry basis, or from at or about 0.5 toat or about 2.5 lb/ream on a dry basis.

An exemplary method for producing a heat transfer label includes thesteps of printing at least 1 layer of an energy curable ink or coatingprovided herein on a substrate, such as on a release layer of a carrierfilm, curing the at least 1 layer of energy curable ink or coating usingactinic radiation to produce a cured print, forming the cured print intoa heat transfer label; and applying the heat transfer label to asubstrate, where the heat transfer label can withstand 25% or morestretch without cracking. Any suitable method can be used to make a heattransfer label as described herein.

An exemplary method of producing a heat transfer label includes thesteps of applying a release layer onto a carrier film, applying at least1 layer of the energy curable high stretch inks or coatings describedherein onto the release layer, curing the at least 1 layer of the ink orcoating using actinic radiation to produce a cured print, and applyingan adhesive layer over the cured print to form a heat transfer label.The ink or coating can be applied by any appropriate method, such aslithographic, flexographic or gravure printing.

Also provided are methods of labelling or decorating an article. Anexemplary method includes providing a support, applying at least 1 layerof the energy curable high stretch inks or coatings described hereinonto the support to form a heat transfer design that can contain a labelor decoration or both, curing the ink or coating of the transfer design,and transferring the heat transfer design from the support to thearticle. The ink or coating is applied by any appropriate method, suchas lithographic, flexographic or gravure printing. The ink or coatingcan be cured by application of ultraviolet radiation or electron beamenergy or a combination thereof. In such methods, transfer of the heattransfer design to the article can include application of heat to theheat transfer design while the heat transfer design is placed intocontact with the article. The methods also can include applying anadhesive layer over the transfer design prior to transfer of the designto the article or applying a release layer to the support prior toapplication of the ink or coating or both of these steps. The methodsare particularly suited for applying a heat transfer label tonon-cylindrical article, such as an article that has at least onecontour or that is tapered.

Also provided are methods of labelling an article with a high stretchheat transfer label. The methods can include as steps providing a highstretch heat transfer label containing at least one layer of the energycurable high stretch inks or coatings described herein, and stretchingat least a portion of the heat transfer label while transferring theheat transfer label to the article in order to improve contact betweenthe heat transfer label and the article. The heat transfer label can bestretched by at least 20% without cracking. In some applications, theHTL can be stretched 25% or more without cracking. In some applications,the stretching step can include application of heat to the heat transferlabel while the heat transfer label is placed into contact with thearticle.

III. EXAMPLES

The following examples, including experiments and results achieved, areprovided for illustrative purposes only and are not to be construed aslimiting the claimed subject matter.

Example 1

Exemplary resin compositions as described herein for use in high-stretchenergy curable ink formulations were prepared. Resin 1 A was prepared bymixing 60 wt % mono functional oligomer, CN131B (an aromaticmonoacrylate oligomer from Sartomer, Exton, Pa.) with 40 wt % inertresin, Laropal® A81 (an aldehyde resin containing a condensation productof urea and aldehydes, from BASF, Cheshire, UK). Resin 1 A contained nomultifunctional monomer or oligomer. Resin IB was prepared by mixing 53wt % mono functional oligomer, CN131B (an aromatic monoacrylate oligomerfrom Sartomer, Exton, Pa.) with 47 wt % inert resin, Laropal® A81 (analdehyde resin containing a condensation product of urea and aldehydes,from BASF, Cheshire, UK). Resin IB contained no multifunctional monomeror oligomer.

Example 2

High-stretch energy curable ink formulations were prepared for use inheat transfer label applications. The formulations provided are merelyrepresentative of the types of materials that can be incorporated intothe inks/coatings and method for use in heat transfer label applicationsof the present application.

Preparation of High-Stretch Energy Curable Ink/Coating Formulations

Exemplary high-stretch energy curable inks were prepared. A clear coat,a process cyan ink, a process magenta ink and a white ink were preparedas described below.

Clear Coat Compositions

A clear coat composition was made according to the following formula bycombining 87% of a resin composition as described herein (Resin 1 A,containing 40% Laropal® A81, a condensation product of urea andaldehydes from BASF, 60% CN131B, a monoacrylate oligomer, and nomultifunctional monomer or multifunctional oligomer) with apolymerization inhibitor (1% Genorad® 16), a viscosity modifier (2%CN131B, an aromatic monoacrylate oligomer); a photoinitiator (4% of a50/50 blend of 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and2-hydroxy-2-methyl-1-phenylpropanone solution), and additives (2% fumedsilica and 4% Micro Talc IT) as shown below in Table 4. The componentswere mixed in a vessel until homogeneous.

TABLE 4 Clear Coat Material Type Supplier % Resin Composition: 87 40%inert resin Laropal ® A81 BASF (condensation product of urea andaldehydes, an inert thermoplastic resin) 60% monofunctional oligomerCN131 B (Aromatic Sartomer monoacrylate oligomer) 0% multifunctionalmonomer or — — oligomer Inhibitor: 1 Polymerization inhibitor Genorad ®16 Rahn Viscosity Modifier: 2 Low viscosity monoacrylate CN131B SartomerPhotoinitiator: 4 Photoinitiator blend 50/50 solution of 2,4,6- SunChemical tri-methylbenzoyl- diphenyl phosphine oxide and2-hydroxy-2-methyl- 1-phenyl propanone Additives: SiO₂ Fumed silicaWacker Silicones Corp. 2 Talc Micro Talc IT Mondo Minerals 4 Total 100

Process Cyan Printing Ink

A process cyan printing ink was made according to the following formulaby combining 58% of a resin composition as described herein (Resin 1A,containing 40% Laropal® A81, a condensation product of urea andaldehydes from BASF, and 60%>CN131B, a monoacrylate oligomer) with apolymerization inhibitor (2% Florstab® UV-1), a viscosity modifier (13%CN13 IB, an aromatic monoacrylate oligomer); a photoinitiator (5% of SUN01), pigment (13% phthalo blue) and additives (1% fumed silica, 4% MicroTalc IT and 4% kaolin clay) as shown below in Table 5. The componentswere mixed in a vessel until homogeneous.

TABLE 5 Process Cyan Ink Material Type Supplier % Resin Composition: 5840% inert resin Laropal ® A81 BASF (condensation product of urea andaldehydes, an inert thermoplastic resin) 60% monofunctional oligomerCN131 B (Aromatic Sartomer monoacrylate oligomer) 0% multifunctionalmonomer or — — oligomer Inhibitor: 2 Polymerization inhibitor Florstab ®UV-1 Kromachem LTD Viscosity Modifier: 13 Low viscosity monoacrylateCN131B Sartomer Photoinitiator: 5 Photoinitiator compound SUN 01 IGMResins, BV Pigment: 13 Blue Pigment Phthalo Blue Sun Chemical Additives:SiO₂ Fumed silica Wacker Silicones Corp. 1 Talc Micro Talc IT MondoMinerals 4 Kaolin Clay Lithosperse ® J. M. Huber Corp. 4 Total 100

Process Magenta Printing Ink

A process magenta printing ink was made according to the followingformula by combining 50.5% of a resin composition as described herein(Resin IB, containing 47% Laropal® A81, a condensation product of ureaand aldehydes from BASF, and 53%>CN131B, a monoacrylate oligomer) with apolymerization inhibitor (2% Florstab® UV-1), a viscosity modifier(13.5% CN131B, an aromatic monoacrylate oligomer); a photoinitiator (10%of SPC1), pigment (20% Irgalite® rubine) and an additive (4% Micro TalcIT) as shown below in Table 6. The components were mixed in a vesseluntil homogeneous.

TABLE 6 Process Magenta Ink Material Type Supplier % Resin Composition:50.5 47% inert resin Laropal ® A81 BASF (condensation product of ureaand aldehydes, an inert thermoplastic resin) 53% monofunctional oligomerCN131 B (Aromatic Sartomer monoacrylate oligomer) 0% multifunctionalmonomer or — — oligomer Inhibitor: 2 Polymerization inhibitor Florstab ®UV-1 Kromachem LTD Viscosity Modifier: 13.5 Low viscosity monoacrylateCN131B Sartomer Photoinitiator: 5 Photoinitiator compound SPC1 SunChemical Pigment: 20 Red Pigment Irgalite ® Rubine Sun ChemicalAdditives: Talc Micro Talc IT Mondo Minerals 4 Total 100

White Printing Ink

A white printing ink was made according to the following formula bycombining 29.0% of a resin composition as described herein (Resin 1 A,containing 40% Laropal® A81, a condensation product of urea andaldehydes from BASF, and 60%>CN131B, a monoacrylate oligomer) with apolymerization inhibitor (0.5% Genorad® 16), a viscosity modifier (11%CN13 IB, an aromatic monoacrylate oligomer); a photoinitiator (4% of SUN01), pigment (50.5% titanium dioxide) and additives (4% Micro Talc ITand 1% fumed silica) as shown below in Table 7. The components weremixed in a vessel until homogeneous.

TABLE 7 White Ink Material Type Supplier % Resin Composition: 29.0 40%inert resin Laropal ® A81 BASF (condensation product of urea andaldehydes, an inert thermoplastic resin) 60% monofunctional oligomerCN131 B (Aromatic Sartomer monoacrylate oligomer) 0% multifunctionalmonomer or — — oligomer Inhibitor: 0.5 Polymerization inhibitorGenorad ® 16 Rahn Viscosity Modifier: 11.0 Low viscosity monoacrylateCN131B Sartomer Photoinitiator: 1.0 Photoinitiator compound SUN01 IGMResins, B.V. Pigment: 50.5 Titanium Dioxide CR286 Tronox Additives: TalcMicro Talc IT Mondo Minerals 4 SiO₂ Fumed silica Wacker Silicones Corp.1 Total 100

Example 3 Test Method for Heat Transfer Labels

The printed heat transfer labels or decorations can be tested fortransferability using any method known in the art. For example, in anexemplary test, the printed heat transfer labels containing thehigh-stretch energy curable inks and/or coatings provided herein weretested on a Therimage Dynacal Model TD-IFC heat transfer decorator3-99-0210-06. In this method, the printed area of the carrier web firstpasses/contacts a preheating plate from the back of the print to beheated to a temperature around 200±50° F., then it passes/contacts asecond plate set at a temperature of 350±50° F. to be further heated,and instantly the second plate also pushes the image area onto thecontainer. The heat activated adhesive of the label or decoration isactivated during this process and the image is transferred to thecontainer with a release layer, such as a wax. It is also possible totransfer without using a release layer.

Test Method for Stretch

During the heat transfer label process described above, the ink is beingstretched. By adjusting the turning speed of the container during thetransfer process, the % stretch can be altered. A simple method ofmeasuring the label before and after stretch allows for easilydetermining the % stretch. For example, if a test portion of the labelis measured at 1 inch before stretch and then 1.25 inch after stretch,it is said to have been stretched by 25% (an increase in length of 25%).The test portion is then assessed for cracking. No visual cracking isconsidered a pass, while visual evidence of cracking (even small cracks)is considered a fail.

For the purposes of testing the inventive inks and method of use in heattransfer labels of the present application HDPE containers were used,but the present application is not limited to this material. Anycommonly known container material or blend of container materials alsocould be used in the container or article to be labeled, includingpolymeric types (such as for example both high and low densityvariations of polyethylene, polypropylene, PETG, PETE, PVC,polycarbonate, acrylic, styrene, etc.); glass types; etc. This includesmaterials used for containers commonly used for consumer goods and seenin consumer markets, such as water, alcoholic beverages, fruit juice,soft drinks, motor oil, cooking oil, medicine, shampoo, cosmetics,personal care products, milk, etc.

Example 4

A series of print trials were performed with several variations toexhibit the ability of the inks and method of the present application toproduce heat transfer labels that can withstand stretching of at least20%, or 25% or more without cracking.

In the examples below, a first down clear coat was first applied on thereleasing layer of a wax coated paper using a Little Joe® proofing pressand then cured by UV light under 200 watt Hg lamp at 150 FPM.Subsequently, 1-3 layers of cyan ink were applied to the cured clearcoat using a Little Joe® proofing press either with inter curing stationor wet-on-wet without inter curing station (cured in one step at theend). Subsequently, a layer of white ink was applied to the cured cyanink layers and cured by UV light under 200 watt Hg lamp at 150 FPM. ThenHydro Heat Seal Adhesive 7MXWF3278, a commercially available water-basedheat activated adhesive, was applied to the cured ink layer. After thewater evaporated and the adhesive dried at room temperature for severalhours until tack free, the print is ready to be tested on a heattransfer decoration machine. All of the high-stretch energy curable inksexhibited good printability, and as indicated by the results below, goodstretchability in the print trials.

Print Trial 1

In Print Trial 1, the heat transfer label was a 3 layer constructionwith inter-station UV cure between ink layers.

Using a Little Joe® proofing press, 6 separate prints were prepared asfollows:

-   Layer 1—a single layer of the clear coat of Example 1 (containing    Resin 1A) followed by cure using a 200 watt Hg lamp at 150 FPM.-   Layer 2—a single layer of process cyan ink of Example 1 (containing    Resin 1A) followed by cure using 200 watt Hg lamp at 150 FPM.-   Layer 3—a single layer of white ink of Example 1 (containing Resin    1A) followed by cure using 200 watt Hg lamp at 150 FPM.-   Layer 4—a single layer of Hydro Heat Seal Adhesive 7MXWF3278.    The resulting prints were then applied as heat transfer labels in    accordance with the Test Method for Heat Transfer Labels described    in Example 2 above and then stretched in accordance with the Test    Method for Stretch described in Example 2 above.

All 6 prints showed no cracking when stretched from 0-25%. Signs ofcracking were seen when prints were stretched to 26% and above.

Example 5 Print Trial 2

In Print Trial 2, the heat transfer label was a 5 layer constructionwith process cyan layers printed wet-on-wet without inter-station curingbetween layers.

Using a Little Joe® proofing press, 4 separate prints were prepared asfollows:

-   Layer 1—a single layer of clear coat of Example 1 (containing Resin    1A) followed by cure using 200 watt Hg lamp at 150 FPM.-   Layers 2, 3, 4—three consecutive single layers of process cyan ink    of Example 1 (containing Resin 1 A) followed by a single cure step    using 200 watt Hg lamp at 150 FPM.-   Layer 5—a single layer of white ink of Example 1 (containing Resin    1A) followed by cure using 200 watt Hg lamp at 150 FPM.-   Layer 6—a single layer of Hydro Heat Seal Adhesive 7MXWF3278. The    prints were then applied as heat transfer labels in accordance with    the Test Method for Heat Transfer Labels described in Example 2    above and then stretched in accordance with the Test Method for    Stretch described in Example 2 above.

Test Results:

All 4 prints showed no cracking when stretched from 0-25%. Signs ofcracking were seen when prints were stretched to 26% and above.

Example 6 Print Trial 3

In Print Trial 3, the heat transfer label was a 5 layer constructionwith inter-station UV curing between layers.

Using a Little Joe® proofing press, 4 separate prints were prepared asfollows:

-   Layer 1—a single layer of clear coat of Example 1 (containing Resin    1A) followed by cure using 200 watt Hg lamp at 150 FPM.-   Layers 2, 3, 4—three consecutive single layers of process cyan ink    of Example 1 (containing Resin 1A) followed by cure using 200 watt    Hg lamp at 150 FPM after each layer.-   Layer 5—a single layer of white ink of Example 1 (containing Resin    1A) followed by cure using 200 watt Hg lamp at 150 FPM.-   Layer 6—a single layer of Hydro Heat Seal Adhesive 7MXWF3278.

The prints were then applied as heat transfer labels in accordance withthe Test Method for Heat Transfer Labels described in Example 2 aboveand then stretched in accordance with the Test Method for Stretchdescribed in Example 2 above.

Test Results:

All 4 prints showed no cracking when stretched from 0-25%. Signs ofcracking were seen when prints were stretched to 26% and above.

Example 7 Comparative Print Trials

For comparative purposes, three separate trials (Trials 4, 5 and 6) wereperformed using Sun Chemical Starluxe® inks, including Starluxe® ProcessCyan, a commercially available heat transfer label ink, printed on thereleasing layer of a wax coated paper. The Starluxe® inks include 25-50%multifunctional acrylates and can contain 10-25% trimethylolpropanetriacrylate and up to 2.5%2-benzyl-2-dimethylamino-4-morpholinobutyrophenone. Thus, thesecommercially available inks include greater than 20 wt % multifunctionalmonomer or multifunctional oligomer. Trial 4: Trial 4 (comparative) wasperformed under the same conditions as used in Trial 1 of Example 4 inthat the heat transfer label was a 3 layer construction withinter-station UV cure between ink layers.

Using a Little Joe® proofing press, 6 separate prints were prepared asfollows:

-   Layer 1—a single layer of Starluxe® Clear Coat followed by cure    using a 200 watt Hg lamp at 150 FPM.-   Layer 2—a single layer of Starluxe® Process Cyan ink followed by    cure using 200 watt Hg lamp at 150 FPM.-   Layer 3—a single layer of Starluxe® White ink followed by cure using    200 watt Hg lamp at 150 FPM.-   Layer 4—a single layer of Hydro Heat Seal Adhesive 7MXWF3278.

The prints were then applied as heat transfer labels in accordance withthe Test Method for Heat Transfer Labels described in Example 2 aboveand then stretched in accordance with the Test Method for Stretchdescribed in Example 2 above.

Test Results:

The prints of Trial 4 exhibited visual cracking when stretched >5%.

Trial 5:

Trial 5 (comparative) was performed under the same conditions as used inTrial 2 of Example 5 in that the heat transfer label was a 5 layerconstruction with process cyan layers printed wet-on-wet withoutinter-station curing between layers.

Using a Little Joe® proofing press, 4 separate prints were prepared asfollows:

-   -   Layer 1—a single layer of Starluxe® Clear Coat followed by cure        using 200 watt Hg lamp at 150 FPM.    -   Layers 2, 3, 4—three consecutive single layers of Starluxe®        Process Cyan ink followed by a single cure step using 200 watt        Hg lamp at 150 FPM.    -   Layer 5—a single layer of Starluxe® White ink followed by cure        using 200 watt Hg lamp at 150 FPM.    -   Layer 6—a single layer of Hydro Heat Seal Adhesive 7MXWF3278.

The prints were then applied as heat transfer labels in accordance withthe Test Method for Heat Transfer Labels described in Example 2 aboveand then stretched in accordance with the Test Method for Stretchdescribed in Example 2 above.

Test Results:

All 4 prints of Trial 5 exhibited visual cracking when stretched >5%.

Trial 6:

Trial 6 (comparative) was performed under the same conditions as used inTrial 3 of Example 6 in that the heat transfer label was a 5 layerconstruction with inter-station UV curing between layers.

Using a Little Joe® proofing press, 4 separate prints were prepared asfollows:

-   -   Layer 1—a single layer of Starluxe® Clear Coat followed by cure        using 200 watt Hg lamp at 150 FPM.    -   Layers 2, 3, 4—three consecutive single layers of Starluxe®        Process Cyan ink followed by cure using 200 watt Hg lamp at 150        FPM after each layer.    -   Layer 5—a single layer of Starluxe® White ink followed by cure        using 200 watt Hg lamp at 150 FPM.    -   Layer 6—a single layer of Hydro Heat Seal Adhesive 7MXWF3278.

The prints were then applied as heat transfer labels in accordance withthe Test Method for Heat Transfer Labels described in Example 2 aboveand then stretched in accordance with the Test Method for Stretchdescribed in Example 2 above.

Test Results:

All 4 prints of Trial 6 exhibited visual cracking when stretched >5%.

In all of the print trials of the Examples, a clear coat was appliedfirst, but this is only one preferred method for producing heat transferlabels and is not a necessity. Heat transfer labels with the clear coatas an intermediate or final layer also is possible. It also would bepossible to produce heat transfer labels without any clear coat or withclear coat as the only layer. Generally, the transfer label includes aclear coat and/or an adhesive layer.

In all of the print trials of the Examples, a process cyan was used asthe non-white ink, but it is understood that other process or spotcolors, such as the process magenta ink described in Example 2, alsocould be used alone or in combination and could be printed in anyconfiguration with other colors or with clear coat or white ink.

In all of the print trials of the Examples, a white coat was appliedlast but this is only a preferred method for producing heat transferlabels and is not a necessity. Heat transfer labels with white as anintermediate or final layer also is possible. It also would be possibleto produce heat transfer labels without any white layer or with white asthe only layer. Generally, the transfer label includes a clear coatand/or an adhesive layer.

The present invention has been described in detail, including thepreferred embodiments thereof, but is more broadly applicable as will beunderstood by those skilled in the art. It will be appreciated thatthose skilled in the art, upon consideration of the present disclosure,may make modifications and/or improvements on this invention that fallwithin the scope and spirit of the invention. Since modifications willbe apparent to those of skill in this art, it is intended that thisinvention be limited only by the scope of the following claims.

What is claimed is:
 1. A high-stretch energy curable resin composition,comprising: a multifunctional monomer or a multifunctional oligomer or acombination thereof in an amount from 0% to 20% based on the weight ofthe energy curable resin composition; and a blend, comprising: an inertresin; and a monofunctional monomer or a monofunctional oligomer or acombination thereof, wherein the blend is present in an amount that is80% or greater based on the weight of the energy curable resincomposition.
 2. The resin composition of claim 1, wherein the blend is asolution comprising an inert resin dissolved in a monofunctional monomeror a monofunctional oligomer or a combination of a monofunctionalmonomer and a monofunctional oligomer.
 3. The resin composition of claim1, wherein the inert resin comprises an inert thermoplastic resin. 4.The resin composition of claim 1, wherein the total amount ofmultifunctional monomer or multifunctional oligomer or combinationthereof is 10 wt % or less than based on the weight of the composition.5. The resin composition of claim 1, wherein the total amount ofmultifunctional monomer or multifunctional oligomer or combinationthereof is 5 wt % less based on the weight of the composition.
 6. Theresin composition of claim 1, wherein the total amount ofmultifunctional monomer or multifunctional oligomer or combinationthereof is 1 wt % or less than based on the weight of the composition.7. The resin composition of claim 1, wherein the multifunctional monomeris a difunctional monomer or oligomer selected from among alkoxylatedaliphatic diacrylate, alkoxylated aliphatic dimethacrylate, alkoxylatedneopentyl glycol diacrylate, alkoxylated neopentyl glycoldimethacrylate, 1,4-butanediol diacrylate, 1,4-butanedioldimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycoldimethacrylate, cyclohexane dimethanol diacrylate, cyclohexanedimethanol dimethacrylate, diethylene glycol diacrylate, diethyleneglycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycoldimethacrylate, 1,12-dodecanediol dimethacrylate, ethoxylated bisphenolA dimethacrylate, ethoxylated (2) bisphenol A dimethacrylate,ethoxylated (3) bisphenol A diacrylate, ethoxylated (4) bisphenol Adiacrylate, ethoxylated (4) bisphenol A dimethacrylate, ethoxylated (6)bisphenol A dimethacrylate, ethoxylated (8) bisphenol A dimethacrylate,ethoxylated (10) bisphenol A diacrylate, ethoxylated (10) bisphenol Adimethacrylate, ethoxylated (30) bisphenol A diacrylate, ethoxylated(30) bisphenol A dimethacrylate, ethylene glycol dimethacrylate,1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol diacrylate, neopentyl glycol dimethacrylate, polyesterdiacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol(400) diacrylate, polyethylene glycol (400) dimethacrylate, polyethyleneglycol (600) diacrylate, polyethylene glycol (600) dimethacrylate,polyethylene glycol dimethacrylate, polypropylene glycol (400)dimethacrylate, propoxylated neopentyl glycol diacrylate, propoxylatedneopentyl glycol dimethacrylate, propoxylated (2) neopentyl glycoldiacrylate, tetraethylene glycol diacrylate, tetraethylene glycoldimethacrylate, tricyclodecane dimethanol diacrylate, triethylene glycoldiacrylate, triethylene glycol dimethacrylate, tripropylene glycoldiacrylate and tripropylene glycol dimethacrylate and combinationsthereof.
 8. The resin composition of claim 1, that contains nomultifunctional monomer or multifunctional oligomer.
 9. The resincomposition of claim 1, wherein the mono functional monomers oroligomers comprise acrylates or methacrylates.
 10. The resin compositionof claim 1, wherein the monofunctional monomers or oligomers have a tackin the range of 8-20.
 11. The resin composition of claim 1, wherein themonofunctional monomers or oligomers have a tack in the range of 10-16.12. The resin composition of claim 1, wherein the monofunctionalmonomers or oligomers have a Tg above 0° C.
 13. The resin composition ofclaim 1, wherein the monofunctional monomers or oligomers have a Tg inthe range of at or about 20° C. to at or about 100° C.
 14. The resincomposition of claim 1, wherein the monofunctional monomers or oligomershave a Tg in the range of at or about 20° C. to 25° C.
 15. The resincomposition of claim 1, wherein the monofunctional monomer ormonofunctional oligomer is selected from among an acrylate ester, anacrylic ester, an acrylic monomer, N-acryloyl amine, N-acryloylmorpholine, aliphatic mono acrylate, aliphatic mono methacrylate,alkoxylated lauryl acrylate, alkoxylated phenol acrylate, alkoxylatedtetrahydrofurfuryl acrylate, C12-C14 alkyl methacrylate, aromaticacrylate monomer, aromatic methacrylate monomer, aromatic monoacrylateoligomer, aromatic monomethacrylate oligomer, benzyl methacrylate,caprolactone acrylate, cyclic trimethylolpropane formal acrylate, cycloaliphatic acrylate monomer, dicyclopentadienyl methacrylate, diethyleneglycol methyl ether methacrylate, epoxy acrylate, epoxy methacrylate,2(2-ethoxy-ethoxy) ethyl acrylate, ethoxylated (4) nonyl phenolacrylate, ethoxylated (4) nonyl phenol methacrylate, ethoxylated nonylphenol acrylate, 2-ethylhexyl methacrylate, isobomyl acrylate, isobomylmethacrylate, isodecyl acrylate, isodecyl acrylate, isodecylmethacrylate, isooctyl acrylate, isooctyl acrylate, lauryl acrylate,lauryl methacrylate, methoxy polyethylene glycol (350) monoacrylate,methoxy polyethylene glycol (350) monomethacrylate, methoxy polyethyleneglycol (550) monoacrylate, methoxy polyethylene glycol (550)monomethacrylate, nonylphenylpolyoxyethylene acrylate, octyldecylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate,polyester acrylate, polyester methacrylate, polyether acrylate,polyether methacrylate, polyphenoxy acrylates, stearyl acrylate, stearylmethacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfurylmethacrylate, tridecyl acrylate, tridecyl methacrylate, triethyleneglycol ethyl ether methacrylate, 3,3,5-trimethylcyclohexyl methacrylate,3,3,5-trimethyl-cyclohexyl methacrylate, urethane acrylate, urethanemethacrylate, an N-vinyl amide, N-vinylformamide and N-vinyl-pyrrolidoneand combinations thereof.
 16. The resin composition of claim 1, whereinthe blend contains an aromatic monoacrylate oligomer.
 17. The resincomposition of claim 1, wherein the inert resin is selected from amongan acrylic resin, a urea aldehyde resin, a polyester resin, an aldehyderesin, an epoxy resin, a rosin ester resin, a cellulose nitrate, acellulose acetobutyrate, a vinyl chloride copolymer, amelamine-formaldehyde resin, a polyurethane resin, a polyimide resin, analkyd resin, an aliphatic phthalate resin and an aromatic phthalateresin and combinations thereof.
 18. The resin composition of claim 1,wherein the inert resin is present in an amount between at or about 10wt % and at or about 90 wt % based on the weight of the resincomposition.
 19. The resin composition of claim 1, wherein the monofunctional monomer is present in an amount between at or about 10 wt %and at or about 90 wt % based on the weight of the resin composition.20. The resin composition of claim 1, further comprising apolymerization inhibitor.
 21. The resin composition of claim 20, whereinthe polymerization inhibitor comprises a benzoquinone, a benzotriazolealuminium salt amine complex, butylated hydroxytoluene, hydroquinone,hydroquinone monomethyl ether, naphthoquinone, t-butylcatechol ort-butylhydroquinone or a combination thereof.
 22. An energy curable inkor coating, comprising the resin composition of claim
 1. 23. A cured inkor coating, comprising the resin composition of claim 1, wherein thecured ink or coating exhibits stretch of 25% or more without cracking.24. The ink or coating of claim 22, wherein the resin composition ispresent in an amount that is from at or about 20% to at or about 80% byweight of the ink or coating.
 25. The ink or coating of claim 22,further comprising a viscosity modifier.
 26. The ink or coating of claim25, wherein the viscosity modifier is present in an amount of at orabout 0.1 wt % to at or about 30 wt % based on the weight of the ink orcoating composition.
 27. The ink or coating of claim 22, furthercomprising a polymerization inhibitor.
 28. The ink or coating of claim27, wherein the polymerization inhibitor comprises a benzoquinone, abenzotriazole aluminium salt amine complex, butylated hydroxytoluene,hydroquinone, hydroquinone monomethyl ether, naphthoquinone,t-butylcatechol or t-butylhydroquinone or a combination thereof.
 29. Theink or coating of claim 27, wherein the polymerization inhibitor ispresent in an amount of at or about 0.1 wt % to at or about 3 wt % basedon the weight of the ink or coating composition.
 30. The ink or coatingof claim 22, further comprising a photoinitiator.
 31. The ink or coatingof claim 30, wherein the photoinitiator comprises benzoin methyl ether,benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethylbenzoin,propylbenzoin, butylbenzoin, pentylbenzoin, benzyl-dimethylketal,2-(o-chlorophenyl)-4,5-diphenylimidazole dimer,2-(o-chloro-phenyl)-4,5-di(m-methoxy-phenyl)imidazole dimer,2-(o-fluorophenyl)-4,5-phenyl-imidazole dimer,2-(o-methoxy-phenyl)-4,5-diphenyl-imidazole dimer,2-(p-methoxy-phenyl)-4,5-diphenyl-imidazole dimer,2,4-di(p-methoxy-phenyl)-5-phenyl-imidazole dimer,2-(2,4-di-methoxyphenyl)-4,5-diphenyl-imidazole dimer,9-phenyl-acridine, 1,7-bis(9,9′-aridinyl)heptane, N-phenyl-glycine,chloro-benzophenone, 4-phenylbenzophenone, trimethyl-benzophenone,3,3′-dimethyl-4-methoxybenzophenone, 4,4′-dimethylamino-benzophenone,4,4′-bis(diethyl-amino)-benzophenone, acrylated benzophenone,methyl-o-benzoyl benzoate, isopropyl-thioxanthone,2-chloro-thioxanthone, 2-ethyl-thioxanthone,2-benzyl-2-(dimethyl-amino)-4′-morpholino-butyrophenone,hydroxybenzophenone, 2,2-dimethoxy-2-phenyl-acetophenone,2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophene,1-hydroxycyclohexylacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone,4-benzoyl-4′-methyl-diphenyl sulfide, ethyl 4-dimethyl-amino-benzoate,2-ethyl-hydroquinone; (2,4,6-trimethylbenzoyl)diphenyl phosphine oxide,ethyl(2,4,6-trimethyl-benzoyl-phenyl phosphinate,1-hydroxy-cyclohexyl-phenyl ketone,2-hydroxy-2-methyl-1-phenylpropanone,2-hydroxy-2-methyl-1-(4-isopropylphenyl)propanone,2-hydroxy-2-methyl-1-(4-dodecylphenyl)propanone,2-hydroxy-2-methyl-1-phenylpropanone,2-hydroxy-2-methyl-1-[(2-hydroxyethoxy)-phenyl]propanone,(2,6-dimethoxy-benzoyl)-2,4,4-tri-methylpentyl phosphine oxide,2,2-dimethoxyl-2-phenyl acetophenone,bis(2,4,6-tri-methylbenzoyl)phenyl-phosphine oxide,bis(2,6-dimethoxybenzoyl)-isooctyl-phosphine oxide orethoxy(2,4,6-trimethyl-benzoyl) phenyl phosphine oxide or a combinationthereof.
 32. The ink or coating of claim 30, wherein the photoinitiatoris present in an amount of at or about 0.1 wt % to at or about 15 wt %based on the weight of the ink or coating composition.
 33. The ink orcoating of claim 22, further comprising a pigment or dye or combinationthereof.
 34. The ink or coating of claim 32, wherein the pigment or dyeor combination thereof is present in an amount of at or about 0.1 wt %to at or about 60 wt % based on the weight of the ink or coatingcomposition.
 35. The ink or coating of claim 22, further comprising anadditive selected from among ammonia, an anti-misting agent, silica,talc, microtalc, clay, a defoamer, a dispersant, a flow agent, alubricant, a wax, a plasticizer, a silicone, a stabilizer and a wettingagent and a combination thereof.
 36. The ink or coating of claim 35,wherein the additive is present in an amount of at or about 0.1 wt % toat or about 15 wt % based on the weight of the ink or coatingcomposition.
 37. An energy curable ink, comprising: 0.1 wt % to 20 wt %pigment/dye; and 30 wt % to 80 wt % of a resin composition of claim 1based on the weight of the ink composition, wherein the ink when curedexhibits stretch of 25% or more without cracking.
 38. An energy curableclear coat, comprising 60 wt %> to 90 wt %> of a resin composition ofclaim 1 based on the weight of the ink composition, wherein the clearcoat when cured exhibits stretch of 25% or more without cracking.
 39. Anenergy curable white ink, comprising: 5 wt %> to 60 wt %> whitepigment/dye; and 20 wt % to 50 wt % of a resin composition of claim 1based on the weight of the ink composition, wherein the white ink whencured exhibits stretch of 25% or more without cracking.
 40. A highstretch heat transfer label, comprising at least one layer of the ink orcoating of claim 22, wherein the label exhibits at least 20% stretchwithout cracking.
 41. The heat transfer label of claim 40, furthercomprising a support portion and a transfer portion.
 42. The heattransfer label of claim 41, wherein the transfer portion comprises oneor more layers of the ink or coating.
 43. The heat transfer label ofclaim 40, further comprising a release layer.
 44. The heat transferlabel of claim 40, further comprising an adhesive layer.
 45. A method ofproducing a high stretch heat transfer label, comprising the steps of:applying a release layer onto a carrier film; applying at least 1 layerof an ink or coating of claim 22 onto the release layer; curing the atleast 1 layer of the ink or coating using actinic radiation to produce acured print; and applying an adhesive layer over the cured print to forma heat transfer label.
 46. The method of claim 45, wherein the ink orcoating is applied by lithographic, flexographic or gravure printing.47. A method of labelling or decorating an article with a high stretchink or coating, comprising: providing a support; applying at least 1layer of an ink or coating of claim 22 on the support to form a heattransfer design comprising a label or decoration or both; curing the inkor coating of the transfer design; and transferring the heat transferdesign from the support to the article.
 48. The method of claim 45,wherein the ink or coating is applied by lithographic, flexographic orgravure printing.
 49. The method of claim 47, wherein the ink or coatingis cured by application of ultraviolet radiation or electron beam energyor a combination thereof.
 50. The method of claim 47, whereintransferring the heat transfer design comprises application of heat tothe heat transfer design while the heat transfer design is placed intocontact with the article.
 51. The method of claim 47, further comprisingapplying an adhesive layer over the transfer design prior to transfer ofthe design to the article.
 52. The method of claim 47, furthercomprising applying a release layer to the support prior to applicationof the ink or coating.
 53. The method of claim 47, wherein the articlehas at least one contour or is tapered.
 54. A method of labelling anarticle with a high stretch heat transfer label, comprising: providing ahigh stretch heat transfer label containing at least one layer of thecured ink or coating of claim 22; and stretching at least a portion ofthe heat transfer label while transferring the heat transfer label tothe article in order to improve contact between the heat transfer labeland the article, wherein the heat transfer label can be stretched by atleast 20% without cracking.
 55. The method of claim 54, wherein thestretching step comprises application of heat to the heat transfer labelwhile the heat transfer label is placed into contact with the article.56. An article, comprising: a label or decoration containing the curedink or coating of claim 22; or a heat transfer label of claim 40.